Biological diversity of Salix taxa in Cu, Pb and Zn phytoextraction from soil.

PubMed

Mleczek, Mirosław; Rutkowski, Paweł; Goliński, Piotr; Kaczmarek, Zygmunt; Szentner, Kinga; Waliszewska, Bogusława; Stolarski, Mariusz; Szczukowski, Stefan

2017-02-01

The aim of the study was to estimate the efficiency of copper (Cu), lead (Pb) and zinc (Zn) phytoextraction by 145 Salix taxa cultivated in an area affected by industrial activity. Survivability and biomass of plants were also analyzed. The highest Cu, Pb and Zn content in shoots was 33.38 ± 2.91 (S. purpurea × viminalis 8), 24.64 ± 1.97 (S. fragilis 1) and 58.99 ± 4.30 (S. eriocephala 7) mg kg -1 dry weight, respectively. In the case of unwashed leaves, the highest content of these metals was 135.06 ± 8.14 (S. purpurea 26), 67.98 ± 5.27 (S. purpurea 45) and 142.56 ± 12.69 (S. alba × triandra 2) mg kg -1 dw, while in washed leaves it was 106.02 ± 11.12 (S. purpurea 45), 55.06 ± 5.75 (S. purpurea 45) and 122.87 ± 12.33 (S. alba × triandra 2) mg kg -1 dw, respectively. The differences between the highest and lowest values for Cu, Pb and Zn were 545%, 20500% and 535% in shoots; 2692%, 2560% and 7500% in unwashed leaves; and 3286%, 2221% and 6950% in washed leaves, respectively. S. acutifolia was able to effectively accumulate all three metals jointly, producing shoots that were well developed in both length and diameter when compared with the other tested willows-an ability that would suggest its high suitability for practical application.

Relation of pH and other soil variables to concentrations of Pb, Cu, Zn, Cd, and Se in earthworms

USGS Publications Warehouse

Beyer, W.N.; Hensler, G.L.; Moore, J.

1987-01-01

Various soil treatments (clay, composted peat, superphosphate, sulfur, calcium carbonate, calcium chloride, zinc chloride, selenous acid) were added to experimental field plots to test the effect of different soil variables on the concentrations of 5 elements in earthworms (Pb, Cu, Zn, Cd, Se). Concentrations of the 5 elements were related to 9 soil variables (soil Pb, soil Cu, soil Zn, pH, organic matter, P, K, Mg, and Ca) with linear multiple regression. Lead concentrations in earthworms were positively correlated with soil Pb and soil organic matter, and negatively correlated with soil pH and soil Mg, with an R2 of 64%. Se concentrations were higher in earthworms from plots amended with Se, and Zn concentrations were higher in earthworms from plots amended with Zn. However, none of the other soil variables had important effects on the concentrations of Cu, Zn, Cd and Se in earthworms. Although some significant statistical relations were demonstrated, the values of r2 of all relations (> 20%) were so low that they had little predictive value.

Distribution of Cd, Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

NASA Astrophysics Data System (ADS)

Du, Ping; Xue, Nandong; Liu, Li; Li, Fasheng

2008-07-01

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40-80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion.

PubMed

Shipley, Heather J; Engates, Karen E; Grover, Valerie A

2013-03-01

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.

Mass change calculations of hydrothermal alterations within the volcanogenic metasediments hosted Cu-Pb (-Zn) mineralization at Halilar area, NW Turkey

NASA Astrophysics Data System (ADS)

Kiran Yildirim, Demet; Abdelnasser, Amr; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Halilar Cu-Pb (-Zn) mineralization that is formed in the volcanogenic metasediments of Bagcagiz Formation at Balikesir province, NW Turkey, represents locally vein-type deposit as well as restricted to fault gouge zone directed NE-SW along with the lower boundary of Bagcagiz Formation and Duztarla granitic intrusion in the study area. Furthermore, This granite is traversed by numerous mineralized sheeted vein systems, which locally transgress into the surrounding metasediments. Therefore, this mineralization closely associated with intense hydrothermal alteration within brecciation, and quartz stockwork veining. The ore mineral assemblage includes chalcopyrite, galena, and some sphalerite with covellite and goethite formed during three phases of mineralization (pre-ore, main ore, and supergene) within an abundant gangue of quartz and calcite. The geologic and field relationships, petrographic and mineralogical studies reveal two alteration zones occurred with the Cu-Pb (-Zn) mineralization along the contact between the Bagcagiz Formation and Duztarla granite; pervasive phyllic alteration (quartz, sericite, and pyrite), and selective propylitic alteration (albite, calcite, epidote, sericite and/or chlorite). This work, by using the mass balance calculations, reports the mass/volume changes (gain and loss) of the chemical components of the hydrothermal alteration zones associated with Halilar Cu-Pb (-Zn) mineralization at Balikesir area (Turkey). It revealed that the phyllic alteration has enrichments of Si, Fe, K, Ba, and LOI with depletion of Mg, Ca, and Na reflect sericitization of alkali feldspar and destruction of ferromagnesian minerals. This zone has high Cu and Pb with Zn contents represents the main mineralized zone. On the other hand, the propylitic zone is characterized by addition of Ca, Na, K, Ti, P, and Ba with LOI and Cu (lower content) referring to the replacement of plagioclase and ferromagnesian minerals by albite, calcite, epidote, and sericite

Spectral analysis of Cu 2+: B 2O 3-ZnO-PbO glasses

NASA Astrophysics Data System (ADS)

Lakshminarayana, G.; Buddhudu, S.

2005-11-01

A new series of heavy metal oxide (PbO) based zinc borate glasses in the chemical composition of (95 - x)B 2O 3-5ZnO- xPbO ( x = 10, 15, 20, 25, 30, 35, 40, 45 and 50 mol%) have been prepared to verify their UV filtering performance. Both direct and indirect optical band gaps ( Eopt) have been evaluated for these glasses. For a reference glass of 45B 2O 3-5ZnO-50PbO, refractive indices at different wavelengths are measured and found the results satisfactorily correlated with the theoretical data upon the computation of Cauchy's constants of A = 1.766029949, B = 159531.024 nm 2 and C = -1.078 × 10 10 nm 4. Measurements concerning X-ray diffraction (XRD), FT-IR, differential scanning colorimeter (DSC) profiles have been carried out for this glass. The FT-IR profile has revealed that the glass has both BO 3 and BO 4 units. From DSC thermogram, glass transition temperature ( Tg), crystallization temperature ( Tc) and melting temperature ( Tm) have been located and from them, other related parameters of the glass have also been calculated. Visible absorption spectra of 45B 2O 3-5ZnO-(50 - x)PbO- xCuO ( x = 0. 1, 0.2, 0.5 and 1.0 mol%) have revealed two absorption bands at around 400 nm ( 2B 1g → 2E g) and 780 nm ( 2B 1g → 2B 2g) of Cu 2+ ions, respectively. Emission bands at 422 and 512 nm are found for the 1 mol% CuO doped glass with excitations at 306 and 332 nm.

Assessment of Ni, Cu, Zn and Pb levels in beach and dune sands from Havana resorts, Cuba.

PubMed

Díaz Rizo, Oscar; Buzón González, Fran; Arado López, Juana O

2015-11-15

Concentrations of nickel (Ni), copper (Cu), zinc (Zn) and lead (Pb) in beach and dune sands from thirteen Havana (Cuba) resorts were estimated by X-ray fluorescence analysis. Determined mean metal contents (in mg·kg(-1)) in beach sand samples were 28±12 for Ni, 35±12 for Cu, 31±11 for Zn and 6.0±1.8 for Pb, while for dune sands were 30±15, 38±22, 37±15 and 6.8±2.9, respectively. Metal-to-iron normalization shows moderately severe and severe enrichment by Cu. The comparison with sediment quality guidelines shows that dune sands from various resorts must be considered as heavily polluted by Cu and Ni. Almost in every resort, the Ni and Cu contents exceed their corresponding TEL values and, in some resorts, the Ni PEL value. The comparison with a Havana topsoil study indicates the possible Ni and Cu natural origin. Copyright © 2015 Elsevier Ltd. All rights reserved.

Counter-current acid leaching process for the removal of Cu, Pb, Sb and Zn from shooting range soil.

PubMed

Lafond, Stéphanie; Blais, Jean-François; Mercier, Guy; Martel, Richard

2013-01-01

This research explores the performance of a counter-current leaching process (CCLP) for Cu, Pb, Sb and Zn extraction in a polluted shooting range soil. The initial metal concentrations in the soil were 1790 mg Cu/kg, 48,300 mg Pb/kg, 840 mg Sb/kg and 368 mg Zn/kg. The leaching process consisted of five one-hour acid leaching steps, which used 1 M H2SO4 + 4 M NaCl (20 degrees C, soil suspension = 100 g/L) followed by two water rinsing steps. Ten counter-current remediation cycles were completed and the average metal removal yields were 98.3 +/- 0.3% of Cu, 99.5 +/- 0.1% of Pb, 75.5 +/- 5.1% of Sb and 29.1 +/- 27.2% of Zn. The quality of metal leaching did not deteriorate throughout the 10 remediation cycles completed for this study. The CCLP reduced acid and salt use by approximately 68% and reduced water consumption by approximately 60%, exceeding reductions achieved by a standard acid leaching process.

Possible Mesozoic age of Ellenville Zn-Pb-Cu(Ag) deposit, Shawangunk Mountains, New York

USGS Publications Warehouse

Friedman, J.D.; Conrad, J.E.; McKee, E.H.; Mutschler, F.E.; Zartman, R.E.

1994-01-01

Ore textures, epithermal open-space filling of Permian structures of the Alleghanian orogeny, and largely postorogenic mineralization of the Ellenville, New York, composite Zn-Pb-Cu(Ag) vein system, provide permissive evidence for post-Permian mineralization. Isochron ages determined by 40Ar/39Ar laser-fusion techniques for K-bearing liquid inclusions in main-stage quartz from the Ellenville deposit additionally suggest a Mesozoic time of mineralization, associated with extensional formation of the Newark basin. The best 40Ar/39Ar total-fusion age range is 165 ?? 30 to 193 ?? 35 Ma. The Mesozoic 40Ar/39Ar age agrees with that of many other dated northern Appalachian Zn-Pb-Cu(Ag) deposits with near-matching lead isotope ratios, and adds new evidence of Jurassic tectonism and mineralization as an overprint to Late Paleozoic tectonism at least as far north as Ellenville (lat. 41??43???N). ?? 1994 Springer-Verlag.

Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

USGS Publications Warehouse

Filipek, L.H.; Chao, T.T.; Carpenter, R.H.

1981-01-01

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh ( Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Influences of traffic on Pb, Cu and Zn concentrations in roadside soils of an urban park in Dublin, Ireland.

PubMed

Dao, Ligang; Morrison, Liam; Zhang, Hongxuan; Zhang, Chaosheng

2014-06-01

Soils in the vicinity of roads are recipients of contaminants from traffic emissions. In order to obtain a better understanding of the impacts of traffic on soils, a total of 225 surface soil samples were collected from an urban park (Phoenix Park, Dublin, Ireland) in a grid system. Metal (Pb, Cu and Zn) concentrations were determined using a portable X-ray fluorescence analyzer. Strong spatial variations for the concentrations of Pb, Cu and Zn were observed. The spatial distribution maps created using geographical information system techniques revealed elevated metal concentrations close to the main traffic route in the park. The relationships between the accumulation of Pb, Cu and Zn in the roadside soils and the distance from the road were well fitted with an exponential model. Elevated metal concentrations from traffic pollution extended to a distance of approximately 40 m from the roadside. The results of this study provide useful information for the management of urban parks particularly in relation to policies aimed at reducing the impact of traffic related pollution on soils.

Distribution of trace metals (Cu, Pb, Ni, Zn) between particulate, colloidal and truly dissolved fractions in wastewater treatment.

PubMed

Hargreaves, Andrew J; Vale, Peter; Whelan, Jonathan; Constantino, Carlos; Dotro, Gabriela; Campo, Pablo; Cartmell, Elise

2017-05-01

The distribution of Cu, Pb, Ni and Zn between particulate, colloidal and truly dissolved size fractions in wastewater from a trickling filter treatment plant was investigated. Samples of influent, primary effluent, humus effluent, final effluent and sludge holding tank returns were collected and separated into particulate (i.e. > 0.45 μm), colloidal (i.e. 1 kDa to 0.45 μm), and truly dissolved (i.e. < 1 kDa) fractions using membrane filters. In the influent, substantial proportions of Cu (60%), Pb (67%), and Zn (32%) were present in the particulate fraction which was removed in conjunction with suspended particles at the works in subsequent treatment stages. In final effluent, sizeable proportions of Cu (52%), Pb (32%), Ni (44%) and Zn (68%) were found within the colloidal size fraction. Calculated ratios of soluble metal to organic carbon suggest the metal to be adsorbed to or complexed with non-humic macromolecules typically found within the colloidal size range. These findings suggest that technologies capable of removing particles within the colloidal fraction have good potential to enhance metals removal from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of alkaline material on phytotoxicity and bioavailability of Cu, Cd, Pb and Zn in stabilized sewage sludge.

PubMed

Zhang, Hongling; Ma, Guofeng; Sun, Lina; Li, Huiying

2017-07-16

The availability and phytotoxicity of heavy metals in sewage sludge is the key restrictive factor that limits sludge application. In this study, municipal sewage sludge was stabilized by alkaline slag or coal fly ash, then the leaching characteristic and fraction distributions of Cu, Cd, Pb and Zn were studied, and their effects on seed germination, root length, and plant accumulating were compared. The results showed that mixed sewage sludge with alkaline slag and coal fly ash decreased the percentage of available heavy metals in sewage sludge. The percentage of exchangeable Cu, Pb, Zn and Cd in stabilized sewage sludge (S1-S4) was 1.50-8.67 times lower than that in SS-only treatment. Leachate Cd, Cu, Pb and Zn from stabilized SS was much lower than the limit threshold. The addition of alkaline materials to SS reduced the inhibitory effect on seed germination and root growth. Pearson's correlation analysis indicated that there was a significant negative correlation between pH and available heavy metals, while a significant positive correlation between the percentage of exchangeable fraction of heavy metals, the leaching potential, tissue concentration and accumulation of heavy metal and toxicity for seed germination was observed.

Electrokinetic enhancement on phytoremediation in Zn, Pb, Cu and Cd contaminated soil using potato plants.

PubMed

Aboughalma, Hanssan; Bi, Ran; Schlaak, Michael

2008-07-01

The use of a combination of electrokinetic remediation and phytoremediation to decontaminate soil polluted with heavy metals has been demonstrated in a laboratory-scale experiment. Potato tubers were planted in plastic vessels filled with Zn, Pb, Cu and Cd contaminated soil and grown in a greenhouse. Three of these vessels were treated with direct current electric field (DC), three with alternative current (AC) and three remained untreated as control vessels. The soil pH varied from anode to cathode with a minimum of pH 3 near the anode and a maximum of pH 8 near the cathode in the DC treated soil profile. There was an accumulation of Zn, Cu and Cd at about 12 cm distance from anode when soil pH was 5 in the DC treated soil profile. There was no significant metal redistribution and pH variation between anode and cathode in the AC soil profile. The biomass production of the plants was 72% higher under AC treatment and 27% lower under DC treatment compared to the control. Metal accumulation was generally higher in the plant roots treated with electrical fields than the control. The overall metal uptake in plant shoots was lower under DC treatment compared to AC treatment and control, although there was a higher accumulation of Zn and Cu in the plant roots treated with electrical fields. The Zn uptake in plant shoots under AC treatment was higher compared to the control and DC treatment. Zn and Cu accumulation in the plant roots under AC and DC treatment was similar, and both were higher comparing to control. Cd content in plant roots under all three treatments was found to be higher than that in the soil. The Pb accumulation in the roots and the uptake into the shoots was lower compared to its content in the soil.

Cd, Cu, Pb and Zn in clams and sediments from an impacted estuary by the oil industry in the southwestern Gulf of Mexico: concentrations and bioaccumulation factors.

PubMed

Ruelas-Inzunza, J; Spanopoulos-Zarco, P; Páez-Osuna, F

2009-12-01

With the objective of estimating the temporal variation and bioavailability of Cd, Cu, Pb and Zn in Coatzacoalcos estuary, the biota-sediment accumulation factors (BSAF) were calculated. For this purpose, surficial sediments and clams from 14 selected sites were collected during three climatic seasons. In surficial sediments, highest levels of Cd and Cu were measured during the rainy season near to the industrial area of Minatitlan, while highest concentrations of Pb and Zn were registered during the windy season in sediments collected near to the industrial area of Coatzacoalcos. Considering all the sampling seasons and bivalve species, average metal concentrations followed the order Zn > Cu > Cd > Pb. BSAF ranged from 0.01 (Pb) in Corbicula fluminea during the hot season to 25.1 (Cd) in Polymesoda caroliniana during the windy season. BSAF of Cd, Cu and Zn were higher during the windy season; in the case of Pb, the dry season was the time when such figure was more elevated. It can be stated that Polymesoda caroliniana is a net accumulator of Cd and Zn and a weak accumulator of Pb for the studied estuary.

Simultaneous determination of Cu 2+, Zn 2+, Cd 2+, Hg 2+ and Pb 2+ by using second-derivative spectrophotometry method

NASA Astrophysics Data System (ADS)

Han, Yanyan; Li, Yan; Si, Wei; Wei, Dong; Yao, Zhenxing; Zheng, Xianpeng; Du, Bin; Wei, Qin

2011-09-01

A new method of simultaneous determination of Cu 2+, Zn 2+, Cd 2+, Hg 2+ and Pb 2+ is proposed here by using the second-derivative spectrophotometry method. In pH = 10.35 Borax-NaOH buffer, using meso-tetra (3-methoxyl-4-hydroxylphenyl) porphyrin ([T-(3-MO-4-HP)P]) as chromomeric reagent, micelle solution was formed after Tween-80 surfactant was added into the solution containing Cu 2+, Zn 2+, Cd 2+, Hg 2+ and Pb 2+ ions. The original absorption spectrum of the above complexes was obtained after heating in the boiling water for 25 min. The second-derivative absorption peaks of five metal-porphyrin complexes can be separated from the original absorption spectrum by using chemometric tool. In this way, Cu 2+, Zn 2+, Cd 2+, Hg 2+ and Pb 2+ ions can be determined simultaneously. Under the optimal conditions, the linear ranges of the calibration curve were 0-0.60, 0-0.60, 0-0.40, 0-0.80 and 0-0.48 μg mL -1 for Cu 2+, Zn 2+, Cd 2+, Hg 2+ and Pb 2+, respectively. The molar absorptivity of these color systems were 1.38 × 10 5, 1.01 × 10 5, 3.24 × 10 5, 1.07 × 10 5 and 1.29 × 10 5 L mol -1 cm -1. The method developed in this paper has advantages in selectivity, sensitivity, operation and can effectively resolve spectra overlapping problem. This method has been applied to determine the real samples with satisfactory results.

Study of the Cu, Mn, Pb and Zn dynamics in soil, plants and bee pollen from the region of Teresina (PI), Brazil.

PubMed

Silva, Aline S; Araújo, Sebastião B; Souza, Darcet C; Silva, Fábio A Santos e

2012-12-01

The purpose of this study is to characterize native bee plants regarding their capacity to extract and accumulate trace elements from the soil and its consequences to the sanity of the produced pollen. The trace elements Cu, Mn, Pb and Zn were analyzed in soil, plants and bee pollen from Teresina region (PI), Brazil, by flame atomic absorption spectrophotometer. Considering the studied plant species, Cu and Pb metals presented in the highest levels in the roots of B. platypetala with 47.35 and 32.71 μg.mL(-1) and H. suaveolens with 39.69 and 17.06 μg.mL(-1), respectively, while in the aerial parts Mn and Zn metals presented the highest levels in S. verticillata with 199.18 and 85.73 μg.mL(-1). In the pollen, the levels of Cu, Mn, Pb and Zn vary from 5.44 to 11.75 μg.mL(-1); 34.31 to 85.75 μg.mL(-1); 13.98 to 18.19 μg.mL(-1) and 50.19 to 90.35 μg.mL(-1), respectively. These results indicate that in the apicultural pasture the translocation (from soil to pollen) of Mn and Zn was more effective than in case of Cu and Pb, therefore, the bee pollen can be used as food supplement without causing risks to human health.

Valorization of a treated soil via amendments: fractionation and oral bioaccessibility of Cu, Ni, Pb, and Zn.

PubMed

Zagury, Gerald J; Rincon Bello, Jhony A; Guney, Mert

2016-04-01

The present study aims to transform a treated soil (TS) into a more desirable resource by modifying physico-chemical properties via amendments while reducing toxic metals' mobility and oral bioaccessibility. A hydrocarbon-contaminated soil submitted to treatment (TS) but still containing elevated concentrations of Cu, Ni, Pb, and Zn has been amended with compost, sand, and Al2(SO4)3 to render it usable for horticulture. Characterization and sequential extraction were performed for TS and four amended mixtures (AM1-4). P and K availability and metal bioaccessibility were investigated in TS and AM2. Amendment improved soil properties for all mixtures and yielded a usable product (AM2 20 % TS, 49 % compost, 30 % sand, 1 % Al2(SO4)3) satisfying regulatory requirements except for Pb content. In particular, AM2 had improved organic matter (OM) and cation exchange capacity (CEC), highly increased P and K availability, and reduced total metal concentrations. Furthermore, amendment decreased metal mobile fraction likely to be plant-available (in mg kg(-1), assumed as soluble/exchangeable + carbonates fractions). For AM2, estimated Pb bioavailability decreased from 1.50 × 10(3) mg kg(-1) (TS) to 238 mg kg(-1) (52.4 % (TS) to 34.2 %). Bioaccessible concentrations of Cu, Ni, and Zn (mg kg(-1)) were lower in AM2 than in TS, but there was no significant decrease for Pb. The results suggest that amendment improved soil by modifying its chemistry, resulting in lower metal mobile fraction (in %, for Cu and Zn) and bioaccessibility (in %, for Cu only). Amending soils having residual metal contamination can be an efficient valorization method, indicating potential for reducing treatment cost and environmental burden by rendering disposal/additional treatment unnecessary. Further studies including plant bioavailability are recommended to confirm results.

Immobilization of Cu, Zn, Cd and Pb in mine drainage stream sediment using Chinese loess.

PubMed

Zang, Fei; Wang, Shengli; Nan, Zhongren; Ma, Jianmin; Li, Yepu; Zhang, Qian; Chen, Yazhou

2017-08-01

The in situ immobilization of metal-contaminated sediment, using various amendments, has attracted great attention owing to their cost-effectiveness. The present study investigated the effectiveness of Chinese loess on Cu, Zn, Cd and Pb stabilization by decreasing their bioavailability in contaminated sediment. The loess was mixed with the sediment in doses of 0, 0.5, 1, 2, 5, 10 and 20 kg. Approximately 70 d after loess application, the effectiveness was evaluated using the Tessier sequential extraction procedure and single extractants, including ethylenediaminetetraacetic acid disodium salt (EDTA-2Na), diethylenetriaminepentaacetic acid (DTPA), calcium chloride (CaCl 2 ) and hydrochloric acid (HCl). The results indicated that the loess can effectively transform Cu from the carbonate fraction into the residual fraction when the loess dose was ≥5 kg. However, loess had little effect on Zn, Cd and Pb immobilization. Correlation analysis showed that these four extractants can provide a good indication of the toxicity of Cu, Zn, Cd and Pb in the amended sediment. Additionally, the organic matter content in the amended sediment decreased by 1.4% for CK, 1.6% for L0.5, 1.7% for L1, 1.5% for L2, 1.5% for L5, 1.9% for L10 and 1.9% for L20 (CK: untreated sediment; L0.5 to L20 represent loess doses of 0.5, 1, 2, 5, 10 and 20 kg, respectively) compared to the initial organic matter content in the unamended sediment, which may increase the atmospheric carbon dioxide owing to the degradation of organic matter. Copyright © 2017 Elsevier Ltd. All rights reserved.

Distribution and mobility of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb) from ammunition residues on shooting ranges for small arms located on mires.

PubMed

Mariussen, Espen; Johnsen, Ida Vaa; Strømseng, Arnljot Einride

2017-04-01

An environmental survey was performed on shooting ranges for small arms located on minerotrophic mires. The highest mean concentrations of Pb (13 g/kg), Cu (5.2 g/kg), Zn (1.1 g/kg), and Sb (0.83 g/kg) in the top soil were from a range located on a poor minerotrophic and acidic mire. This range had also the highest concentrations of Pb, Cu, Zn, and Sb in discharge water (0.18 mg/L Pb, 0.42 mg/L Cu, 0.63 mg/L Zn, and 65 μg/L Sb) and subsurface soil water (2.5 mg/L Pb, 0.9 mg/L Cu, 1.6 mg/L Zn, and 0.15 mg/L Sb). No clear differences in the discharge of ammunition residues between the mires were observed based on the characteristics of the mires. In surface water with high pH (pH ~7), there was a trend with high concentrations of Sb and lower relative concentrations of Cu and Pb. The relatively low concentrations of ammunition residues both in the soil and soil water, 20 cm below the top soil, indicates limited vertical migration in the soil. Channels in the mires, made by plant roots or soil layer of less decomposed materials, may increase the rate of transport of contaminated surface water into deeper soil layers and ground water. A large portion of both Cu and Sb were associated to the oxidizable components in the peat, which may imply that these elements form inner-sphere complexes with organic matter. The largest portion of Pb and Zn were associated with the exchangeable and pH-sensitive components in the peat, which may imply that these elements form outer-sphere complexes with the peat.

The potential of Lemna gibba L. and Lemna minor L. to remove Cu, Pb, Zn, and As in gallery water in a mining area in Keban, Turkey.

PubMed

Sasmaz, Merve; Arslan Topal, Emine Işıl; Obek, Erdal; Sasmaz, Ahmet

2015-11-01

This study was designed to investigate removal efficiencies of Cu, Pb, Zn, and As in gallery water in a mining area in Keban, Turkey by Lemna gibba L. and Lemna minor L. These plants were placed in the gallery water of Keban Pb-Zn ore deposits and adapted individually fed to the reactors. During the study period (8 days), the plant and water samples were collected daily and the temperature, pH, and electric conductivity of the gallery water were measured daily. The plants were washed, dried, and burned at 300 °C for 24 h in a drying oven. These ash and water samples were analyzed by ICP-MS to determine the amounts of Cu, Pb, Zn, and As. The Cu, Pb, Zn and As concentrations in the gallery water of the study area detected 67, 7.5, 7230, and 96 μg L(-1), respectively. According to the results, the obtained efficiencies in L. minor L. and L. gibba L. are: 87% at day 2 and 36% at day 3 for Cu; 1259% at day 2 and 1015% at day 2 for Pb; 628% at day 3 and 382% at day 3 for Zn; and 7070% at day 3 and 19,709% at day 2 for As, respectively. The present study revealed that both L. minor L. and L. gibba L. had very high potential to remove Cu, Pb, Zn, and As in gallery water contaminated by different ores. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Competitive adsorption of Pb(II), Cu(II), and Zn(II) ions onto hydroxyapatite-biochar nanocomposite in aqueous solutions

NASA Astrophysics Data System (ADS)

Wang, Yu-Ying; Liu, Yu-Xue; Lu, Hao-Hao; Yang, Rui-Qin; Yang, Sheng-Mao

2018-05-01

A hydroxyapatite-biochar nanocomposite (HAP-BC) was successfully fabricated and its physicochemical properties characterized. The analyses showed that HAP nanoparticles were successfully loaded on the biochar surface. The adsorption of Pb(II), Cu(II), and Zn(II) by HAP-BC was systematically studied in single and ternary metal systems. The results demonstrated that pH affects the adsorption of heavy metals onto HAP-BC. Regarding the adsorption kinetics, the pseudo-second-order model showed the best fit for all three heavy metal ions on HAP-BC. In both single and ternary metal ion systems, the adsorption isotherm of Pb(II) by HAP-BC followed Langmuir model, while those of Cu(II) and Zn(II) fitted well with Freundlich model. The maximum adsorption capacity for each tested metal by HAP-BC was higher than that of pristine rice straw biochar (especially for Pb(II)) or those of other reported adsorbents. Therefore, HAP-BC could explore as a new material for future application in heavy metal removal.

Potential hyperaccumulation of Pb, Zn, Cu and Cd in endurant plants distributed in an old smeltery, northeast China

NASA Astrophysics Data System (ADS)

Cui, Shuang; Zhou, Qixing; Chao, Lei

2007-01-01

The absorption and accumulation of Pb, Zn, Cu and Cd in some endurant weed plant species that survived in an old smeltery in Liaoning, China, were systematically investigated. Potential hyperaccumulative characteristics of these species were also discussed. The results showed that metal accumulation in plants differed with species, tissues and metals. Endurant weed plants growing in this contaminated site exhibited high metal adaptability. Both the metal exclusion and detoxification tolerance strategies were involved in the species studied. Seven species for Pb and four species for Cd were satisfied for the concentration time level standard for hyperaccumulator. Considering translocation factor (TF) values, one species for Pb, seven species for Zn, two species for Cu and five species for Cd possessed the characteristic of hyperaccumulator. Particularly, Abutilon theophrasti Medic, exhibited strong accumulative ability to four heavy metals. Although enrichment coefficients of all samples were lesser than 1 and the absolute concentrations didn’t reach the standard, species mentioned above were primarily believed to be potential hyperaccumulators.

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions.

PubMed

Cao, Xinde; Liang, Yuan; Zhao, Ling; Le, Huangying

2013-09-01

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P + T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn > Cu > Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P + T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic

Effect of bamboo and rice straw biochars on the mobility and redistribution of heavy metals (Cd, Cu, Pb and Zn) in contaminated soil.

PubMed

Lu, Kouping; Yang, Xing; Gielen, Gerty; Bolan, Nanthi; Ok, Yong Sik; Niazi, Nabeel Khan; Xu, Song; Yuan, Guodong; Chen, Xin; Zhang, Xiaokai; Liu, Dan; Song, Zhaoliang; Liu, Xingyuan; Wang, Hailong

2017-01-15

Biochar has emerged as an efficient tool to affect bioavailability of heavy metals in contaminated soils. Although partially understood, a carefully designed incubation experiment was performed to examine the effect of biochar on mobility and redistribution of Cd, Cu, Pb and Zn in a sandy loam soil collected from the surroundings of a copper smelter. Bamboo and rice straw biochars with different mesh sizes (<0.25 mm and <1 mm), were applied at three rates (0, 1, and 5% w/w). Heavy metal concentrations in pore water were determined after extraction with 0.01 M CaCl 2 . Phytoavailable metals were extracted using DTPA/TEA (pH 7.3). The European Union Bureau of Reference (EUBCR) sequential extraction procedure was adopted to determine metal partitioning and redistribution of heavy metals. Results showed that CaCl 2 -and DTPA-extractable Cd, Cu, Pb and Zn concentrations were significantly (p < 0.05) lower in the bamboo and rice straw biochar treated soils, especially at 5% application rate, than those in the unamended soil. Soil pH values were significantly correlated with CaCl 2 -extractable metal concentrations (p < 0.01). The EUBCR sequential extraction procedure revealed that the acid extractable fractions of Cd, Cu, Pb and Zn decreased significantly (p < 0.05) with biochar addition. Rice straw biochar was more effective than bamboo biochar in decreasing the acid extractable metal fractions, and the effect was more pronounced with increasing biochar application rate. The effect of biochar particle size on extractable metal concentrations was not consistent. The 5% rice straw biochar treatment reduced the DTPA-extractable metal concentrations in the order of Cd < Cu < Pb < Zn, and reduced the acid extractable pool of Cd, Cu, Pb and Zn by 11, 17, 34 and 6%, respectively, compared to the control. In the same 5% rice straw biochar treatments, the organic bound fraction increased by 37, 58, 68 and 18% for Cd, Cu, Pb and Zn, respectively, compared to the

Determination of some heavy metals (Fe, Cu, Zn and Pb) in blood by total reflection X-ray fluorescence

NASA Astrophysics Data System (ADS)

Bounakhla, M.; Doukkali, A.; Lalaoui, K.; Aguenaou, H.; Mokhtar, N.; Attrassi, B.

2003-05-01

The main purpose of this study is the interaction between nutrition (micronutrients heavy metals: Fe, Zn, Cu) and toxic heavy metals such as Pb in blood of children living in Gharb region of Morocco. This region receives all pollution carried by the Sebou river coming mainly from industrial activities. A rapid and simple analytical procedure was used for the determination of Fe, Cu and Zn trace amounts in blood by total-reflection X-ray fluorescence technique. This method is an energy dispersive XRF technique in a special geometry of primary beam, sample and detector. The sample is deposited on a plane polished surface of a suitable reflector material. It is presented as a few drops (25 μl) from a solution of blood digested in a mixture of HNO3 and H2O2 using a microwaves accelerated reaction system. The accuracy of measurements has been investigated by using certified materials. The concentration of Cu was found to be normal in all samples (\\cong1 ppm) which ruled out any interaction between this element and the others. On the other hand, amounts of Fe and Zn are very variables, suggesting an interaction between Fe and Zn. However, amounts of Pb in blood are inferior to 50 ppb, suggesting that no interaction exist with this metal and micronutrients.

[Effects of fly ash on the exchangeable heavy metals (Cu, Zn, Pb) during sewage sludge composting and land utilization].

PubMed

Sheng, Jun; Lu, Wen-Jing; Wang, Hong-Tao

2007-06-01

A series of composting test using fly ash as stabilizing agent were investigated to study the variation of the exchangeable heavy metals during composting and land utilization. A whole procedure of adsorption and desorption of stabilized heavy metals were analyzed. The result shows that the exchangeable Cu increases while the exchangeable Zn and Pb decrease during composting. Fly ash has significant stabilizing effect on Zn and Pb as evidenced by a decline of 62.47% and 92.61% respectively in the trails with flay ash as stabilizing agent. However there is no obvious change with exchangeable Cu. Although there is a big difference on the activities of heavy metals in different soil types tested, it seems to be ineluctable that addition of sewage sludge composting products cause enrichment of heavy metal in soil.

Mineral potential tracts for polymetallic Pb-Zn-Cu vein deposits (phase V, deliverable 71): Chapter I in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Beaudoin, Georges

2015-01-01

In Mauritania, mineral occurrences of the polymetallic Pb-Zn-Cu vein deposit type are found near the Florence-El Khdar shear zone in northeast Mauritania. The deposits visited were deemed representative of other similar occurrences and consist of quartz veins with trace sulfides. The low sulfide and Pb-Zn-Cu content in the quartz veins is unlike producing polymetallic Pb-Zn-Cu vein deposits, such that the veins are not considered to belong to this deposit type. Mineral potential tracts for polymetallic Pb-ZnCu veins are highly speculative considering the lack of known mineralization belonging to this deposit type. Mineral potential tracts for polymetallic Pb-Zn-Cu veins are associated with and surround major shear zones in the Rgueïbat Shield and zones of complex faulting in the southern Mauritanides, at the exclusion of the imbricated thrust faults that are not considered favorable for this deposit type. No skarn and replacement deposits have been documented in Mauritania and the low mineral potential is indicated by lack of causative Mesozoic and Cenozoic mafic to felsic stocks.

Paleomagnetic dating of the Cu-Zn-Pb Kupferschiefer deposit at Sangerhausen, Germany

NASA Astrophysics Data System (ADS)

Symons, D. T.; Kawasaki, K.; Walther, S.; Borg, G.

2010-12-01

Paleomagnetic and rock magnetic results are reported for the Cu-Zn-Pb Kupferschiefer mineralization at Sangerhausen, Germany. The mineralization is richest in the ~0.5 m thick Upper Permian (258±2 Ma) Kupferschiefer black marly shale (9 sites) and dies out over ~0.2 m in the underlying Weisliegend sandstones (3 sites) and overlying Zechstein carbonates (2 sites). Paleomagnetic and rock magnetic analysis were made on 205 specimens from 15 sites on the margin of the Sangerhausen Syncline. Except for the one site from fault zone gypsum, stable characteristic remanent magnetization (ChRM) directions were isolated in pyrrhotite with minor magnetite for the 14 sites using alternating field and thermal step demagnetization. Rock magnetic measurements show that the Kupferschiefer shale marks a redox front between the oxidized Weissliegend sandstones and non-oxidized Zechstein carbonates. A negative paleomagnetic fold test indicates that the ChRM postdates Jurassic fault block tilting. The ChRM directions from the 14 sites give a Late Jurassic paleopole at 149±3 Ma on the European apparent polar wander path. The observed age is significantly younger than the 254±6 Ma primary age of the associated red beds near Lubin in Poland, based on re-interpretation of the 1987 paleopole of Jowett et al. Overall the paleomagnetic results at Sangerhausen favour a very late diagenetic or epigenetic Late Jurassic origin for the Cu-Pb-Zn mineralization in the Kupferschiefer rather than the commonly proposed Late Permian syngenetic to mid-Triassic diagenetic origin.

Contents and leachability of heavy metals (Pb, Cu, Sb, Zn, As) in soil at the Pantex firing range, Amarillo, Texas.

PubMed

Basunia, S; Landsberger, S

2001-10-01

Pantex firing range soil samples were analyzed for Pb, Cu, Sb, Zn, and As. One hundred ninety-seven samples were collected from the firing range and vicinity area. There was a lack of knowledge about the distribution of Pb in the firing range, so a random sampling with proportional allocation was chosen. Concentration levels of Pb and Cu in the firing range were found to be in the range of 11-4675 and 13-359 mg/kg, respectively. Concentration levels of Sb were found to be in the range of 1-517 mg/kg. However, the Zn and As concentration levels were close to average soil background levels. The Sn concentration level was expected to be higher in the Pantex firing range soil samples. However, it was found to be below the neutron activation analysis (NAA) detection limit of 75 mg/kg. Enrichment factor analysis showed that Pb and Sb were highly enriched in the firing range with average magnitudes of 55 and 90, respectively. Cu was enriched approximately 6 times more than the usual soil concentration levels. Toxicity characteristic leaching procedure (TCLP) was carried out on size-fractionated homogeneous soil samples. The concentration levels of Pb in leachates were found to be approximately 12 times higher than the U.S. Environmental Protection Agency (EPA) regulatory concentration level of 5 mg/L. Sequential extraction (SE) was also performed to characterize Pb and other trace elements into five different fractions. The highest Pb fraction was found with organic matter in the soil.

Differential Metal Tolerance and Accumulation Patterns of Cd, Cu, Pb and Zn in the Liverwort Marchantia polymorpha L.

PubMed

Ares, Ángela; Itouga, Misao; Kato, Yukari; Sakakibara, Hitoshi

2018-03-01

In this study, we investigated the bioaccumulation, tissue distribution and physiological responses to different metal concentration (0.2 and 2 mM) and time of exposure of 1, 2 and 3 weeks with cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) using the model liverwort Marchantia polymorpha. Our data showed, on one hand, a significant enrichment and tissue translocation of Cu, Zn, and specially Cd, reaching concentrations of 1800 µg g - 1 in 3 weeks. On the other hand, Pb exhibited the lowest concentration values (50 µg g - 1 ), and 90% of the total concentration in the rhizoids. We could observe a positive correlation between tissue concentration, metal translocation and an enhanced toxic response. The results obtained in this study might contribute not only in the application of this species in environmental studies with heavy metals but also as a starting point to study the evolution of metal tolerance in land plants.

Stabilization of Cd-, Pb-, Cu- and Zn-contaminated calcareous agricultural soil using red mud: a field experiment.

PubMed

Wang, Yangyang; Li, Fangfang; Song, Jian; Xiao, Ruiyang; Luo, Lin; Yang, Zhihui; Chai, Liyuan

2018-04-12

Red mud (RM) was used to remediate heavy metal-contaminated soils. Experiments with two different dosages of RM added to soils were carried out in this study. It was found that soil pH increased 0.3 and 0.5 unit with the dosage of 3 and 5% (wt%), respectively. At the dosage of 5%, the highest stabilization efficiencies for Cd, Pb, Cu and Zn reached 67.95, 64.21, 43.73 and 63.73%, respectively. The addition of RM obviously transferred Cd from the exchangeable fraction to the residual fraction. Meanwhile, in comparison with the control (no RM added), it reduced 24.38, 49.20, 19.42 and 8.89% of Cd, Pb, Cu and Zn in wheat grains at the RM addition dosage of 5%, respectively. At the same time, the yield of wheat grains increased 17.81 and 24.66% at the RM addition dosage of 3 and 5%, respectively. Finally, the addition of RM did not change the soil bacterial community. These results indicate that RM has a great potential in stabilizing heavy metals in calcareous agricultural soils.

Mineralogical and geochemical characterization of supergene Cu-Pb-Zn-V ores in the Oriental High Atlas, Morocco

NASA Astrophysics Data System (ADS)

Verhaert, Michèle; Bernard, Alain; Dekoninck, Augustin; Lafforgue, Ludovic; Saddiqi, Omar; Yans, Johan

2017-10-01

In the Moroccan High Atlas, two sulfide deposits hosted by Jurassic dolostones underwent significant weathering. In the Cu deposit of Jbel Klakh, several stages of supergene mineralization are distinguished: (1) the replacement of hypogene sulfides in the protolith (chalcopyrite) by secondary sulfides in the cementation zone (bornite, digenite, chalcocite, covellite), (2) the formation of oxidized minerals in the saprolite (malachite, azurite, brochantite) where the environment becomes more oxidizing and neutral, and (3) the precipitation of late carbonates (calcite) and iron (hydr-)oxides in the laterite. The precipitation of carbonates is related to the dissolution of dolomitic host rocks, which buffers the fluid acidity due to the oxidation of sulfides. In the Jbel Haouanit Pb-Zn deposit, the mineral assemblage is dominated by typical calamine minerals, Cu minerals (chalcocite, covellite, malachite), and a Cu-Pb-Zn vanadate (mottramite). Galena is successively weathered in anglesite and cerussite. Sphalerite is weathered in smithsonite, which is rapidly replaced by hydrozincite. Late iron (hydr-)oxides are mainly found at the top of both deposits (laterite). Both deposits are thus characterized by specific mineral zoning, from laterite to protolith, related to variations in the mineralogy and ore grades and probably caused by varying Eh-pH conditions.

Mobility of Pb, Zn, Cu and As in disturbed forest soils affected by acid rain.

PubMed

Kochergina, Yulia V; Udatný, Martin; Penížek, Vít; Mihaljevič, Martin

2017-10-18

Early efforts at remediation of contaminated soils involve overturn or removal of the uppermost soil horizons. We find that such disruption is counterproductive, as it actually increases the mobility of the heavy metals involved. In our study, we sought to replicate in a controlled manner this commonly used remediation strategy and measure Pb, Zn, Cu and As concentrations in all soil horizons-both prior to and 1 year after disruption by trenching. BCR analyses (sequential leaching) indicate that Pb is affected to the greatest degree and is most highly mobile; however, Zn and As remain insoluble, thus partially ameliorating the detrimental effect. Differences in vegetation cover (i.e. spruce vs. beech forest) have little influence on overall element mobility patterns. The Krušné hory (Ore Mts., Czech Republic) study area is one of the more heavily contaminated areas in Central Europe, and thus the results reported here are applicable to areas affected by brown-coal-burning power plants.

Assessment of metal concentrations (Cu, Zn, and Pb) in seawater, sediment and biota samples in the coastal area of Eastern Black Sea, Turkey.

PubMed

Baltas, Hasan; Sirin, Murat; Dalgic, Goktug; Bayrak, Esra Yilmaz; Akdeniz, Aysel

2017-09-15

This study investigated the contents of Cu, Zn and Pb in seawater, sediment, different shell sizes of mussel (Mytilus galloprovincialis) and sea snail (Rapana venosa) samples collected from four different provinces of the Eastern Black Sea Region. With the exception of Zn, all the metal concentration values measured in the sea snail were observed to be higher than those of mussels in all stations. While the correlation between mussels and sea snail according to metal concentrations was found to be positive (p˂0.05), this relation was not observed between the other parameters, such as the shell sizes, salinity and pH (p˃0.05). Although the mean concentration values of Cu, Zn, and Pb for mussel and sea snail are significantly above the tolerable levels, the estimated daily intake values for mussel were below the daily intake recommended. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dynamic adsorption of mixtures of Rhodamine B, Pb (II), Cu (II) and Zn(II) ions on composites chitosan-silica-polyethylene glycol membrane

NASA Astrophysics Data System (ADS)

Mahatmanti, F. W.; Rengga, W. D. P.; Kusumastuti, E.; Nuryono

2018-04-01

The adsorption of a solution mixture of Rhodamine B, Pb (II), Cu (II) and Zn(II) was studied using dynamic methods employing chitosan-silica-polyethylene glycol (Ch/Si/P) composite membrane as an adsorptive membrane. The composite Ch/Si/P membrane was prepared by mixing a chitosan-based membrane with silica isolated from rice husk ash (ASP) and polyethylene glycol (PEG) as a plasticizer. The resultant composite membrane was a stronger and more flexible membrane than the original chitosan-based membrane as indicated by the maximum percentage of elongation (20.5 %) and minimum Young’s Modulus (80.5 MPa). The composite membrane also showed increased mechanical and hydrophilic properties compared to the chitosan membranes. The membrane was used as adsorption membrane for Pb (II), Cu (II), Cd (II) ions and Rhodamine B dyes in a dynamic system where the permeation and selectivity were determined. The permeation of the components was observed to be in the following order: Rhodamine B > Cd (II) > Pb (II) > Cu (II) whereas the selectivity was shown to decrease the order of Cu (II) > Pb (II) > Cd (II) > Rhodamine B.

Coexistence of Cu, Fe, Pb, and Zn oxides and chlorides as a determinant of chlorinated aromatics generation in municipal solid waste incinerator fly ash.

PubMed

Fujimori, Takashi; Tanino, Yuta; Takaoka, Masaki

2014-01-01

We investigated chemical determinants of the generation of chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs), in fly ash from municipal solid waste incineration. The influences of the following on aromatic-Cls formation in model fly ash (MFA) were systematically examined quantitatively and statistically: (i) inorganic chlorides (KCl, NaCl, CaCl2), (ii) base materials (SiO2, Al2O3, CaCO3), (iii) metal oxides (CuO, Fe2O3, PbO, ZnO), (iv) metal chlorides (CuCl2, FeCl3, PbCl2, ZnCl2), and (v) "coexisting multi-models." On the basis of aromatic-Cls concentrations, the ∑CBzs/∑PCBs ratio, and the similarity between distribution patterns, MFAs were categorized into six groups. The results and analysis indicated that the formation of aromatic-Cls depended strongly on the "coexistence condition", namely multimodels composed of not only metal chlorides, but also of metal oxides. The precise replication of metal chloride to oxide ratios, such as the precise ratios of Cu-, Fe-, Pb-, and Zn-chlorides and oxides, may be an essential factor in changing the thermochemical formation patterns of aromatic-Cls. Although CuCl2 acted as a promoter of aromatic-Cls generation, statistical analyses implied that FeCl3 also largely influenced the generation of aromatic-Cls under mixture conditions. Various additional components of fly ash were also comprehensively analyzed.

Zinc, copper, and lead in mid-ocean ridge basalts and the source rock control on Zn/Pb in ocean-ridge hydrothermal deposits

USGS Publications Warehouse

Doe, B.R.

1994-01-01

The contents of Zn, Cu, and Pb in mid-ocean ridge basalts (MORB) and the MORB source-rock control on Zn/Pb in ocean-ridge hydrothermal deposits are examined. The values of Zn, Cu, and Pb for submarine mid-ocean ridge basalts (MORB) are, respectively (in ppm): average MORB-75, 75, and 0.7; West Valley, Juan de Fuca Ridge (JFR)-87, 64, and 0.5; southern JFR-120 and 0.5; and 21??N, East Pacific Rise (EPR)-73, 78, and 0.5. Values of Zn/Pb range from about 100-240 and Cu/ Pb from 100-156. In this study, Zn is found to correlate positively with TiO2 + FeO (mean square of weighted deviates, MSWD, of 1.6 for JFR basalt), and inversely with Mg number (MSWD of 3.5). Therefore, contrary to statements in the literature that Zn should be compatible in MORB, Zn is a mildly incompatible element and must be enriched in the glass phase relative to olivine as Zn does not fit into the other major phenocryst phase, plagioclase. In the source of MORB, Zn likely is most enriched in oxides: spinel, magnetite, and titanomagnetite. Copper generally does not correlate well with other elements in most MORB data examined. When differentiation is dominated by olivine, Cu has a tendency to behave incompatibly (e.g., at Mg numbers > 70), but, overall, Cu shows some tendency towards being a compatible element, particularly along the Mid-Atlantic Ridge, a behavior presumably due to separation of sulfides in which Cu (but not Zn) is markedly enriched. Copper thus may be in dispersed sulfides in the source of MORB. Ocean ridges provide important data on source-rock controls for sulfide deposits because, in sediment-starved ridges, much is known about the possible source rocks and mineralization is presently occurring. In contrast to Zn/Pb ~5 in continental hot Cl-rich brines, Zn/Pb in the hottest sediment-starved ridge black smoker hydrothermal fluids at 21 ??N, EPR is about 110, similar to local MORB (145), but Cu/Pb is closer to 30, possibly due to subsurface deposition of Cu. At the JFR, the best

Multi-component sorption of Pb(II), Cu(II) and Zn(II) onto low-cost mineral adsorbent.

PubMed

Prasad, Murari; Xu, Huan-yan; Saxena, Sona

2008-06-15

Multi-component sorption studies were carried out for attenuation of divalent heavy metal cations (Pb2+, Cu2+ and Zn2+) by a low-cost mineral adsorbent from the aqueous solution. Kinetic and equilibrium batch-type sorption experiments were conducted under variable conditions for multi-component using low-grade (<12%P2O5) phosphate rock. Percentage of multiple heavy metal species removal increases with decreasing initial metals concentration and particle size. The equilibrium data were well described to a lesser extent by Freundlich model but Langmuir model seemed to be more appropriate with the fixation capacity obtained at room temperature for Pb2+, Cu2+ and Zn2+ was 227.2, 769.2 and 666.6 micromol g(-1), respectively. Two simple kinetic models were tested to investigate the adsorption mechanism. Rate constants have been found nearly constant at all metal concentrations for first order. The comparison of adsorption capacity of low-grade phosphate rock decreases in multi-component system as compared to single component due to ionic interactions. X-ray powder diffraction (XRPD) technique was used to ascertain the formation of new metal phases followed by surface complexation. Used adsorbents have been converted into a value added product by utilizing innovative Zero-waste concept to solve the used adsorbents disposal problem and thus protecting the environment.

Yield strength of Cu and a CuPb alloy (1% Pb)

NASA Astrophysics Data System (ADS)

Buttler, W. T.; Gray, G. T.; Fensin, S. J.; Grover, M.; Prime, M. B.; Stevens, G. D.; Stone, J. B.; Turley, W. D.

2017-01-01

With PBX9501 we explosively loaded fully annealed OFHC-Cu and an OFHC-CuPb (extruded with 1% Pb that aggregates at the Cu grain boundaries) to study the effects of the 1% Pb on the elastic-plastic yield Y of Cu. The yield-stress Y was studied through observation of surface velocimetry and total ejected mass ρA from periodic surface perturbations machined onto the sample surfaces. The perturbation's wavelengths were λ ≈ 65 µm, and their amplitudes h were varied to determine the wavenumber (2π/λ) amplitude product kh at which ejecta production for the Cu and CuPb begins, which relates to Y. The Y of the two materials is apparently different.

Analysis of Zn, Cd, As, Cu, Pb, and Fe in snails as bioindicators and soil samples near traffic road by ICP-OES.

PubMed

Massadeh, Adnan M; Alomary, Ahmed A; Mir, Sayeeda; Momani, Fouad A; Haddad, Hazem I; Hadad, Yazen A

2016-07-01

Snails are used as biological indicators of the environment pollution for heavy metals. Living snail samples were collected from different sites at the city of Irbid-Jordan and classified according to their morphological features including Helix pelasga, Eobania vermiculata, Xeropicta derbentina, Oychilus, Xerocrassa seetzenii, Xerocrassa simulata, and Pila. Zn, Cd, As, Cu, Pb, and Fe levels were measured by inductively coupled plasma-optical emission spectroscopy. Results indicated that metal concentrations in all snail shell samples were with an average and range for Zn 22.4 (6.5-105.5) μg g(-1), Cd 7.8 (0.4-48.1) μg g(-1), As 25.9 (0.7-248.5) μg g(-1), Cu 15.1 (1.6-69.0) μg g(-1), Pb 0.4 (0.2-1.7) μg g(-1), and Fe 119.6 (14.0-1102.0) μg g(-1), whereas, in soil samples, the average and range for Zn 204.0 (12.0-709.0) μg g(-1), Cd 5.7 (0.2-39.5) μg g(-1), As 3.2 (1.8-5.2) μg g(-1), Cu 22.1 (2.3-77.4) μg g(-1), Pb 0.2 (0.1-0.3) μg g(-1), and Fe 242.4 (25.0-680.0) μg g(-1).

Silver-bearing minerals in the Xinhua hydrothermal vein-type Pb-Zn deposit, South China

NASA Astrophysics Data System (ADS)

Wang, Minfang; Zhang, Xubo; Guo, Xiaonan; Pi, Daohui; Yang, Meijun

2018-02-01

Electron probe microanalysis (EPMA) results are reported for newly identified silver-bearing minerals from the Xinhua deposit, Yunkaidashan area, South China. The Xinhua deposit is a hydrothermal vein-type Pb-Zn deposit and is hosted in the Pubei Complex, which consists of a cordierite-biotite granite with a U-Pb zircon age of 244.3 ± 1.8-251.9 ± 2.2 Ma. The mineralization process is subdivided into four mineralization stages, characterized by the following mineral associations: mineralization stage I with quartz, pyrite, and sphalerite; mineralization stage II with siderite, galena, and tetrahedrite; mineralization stage III with quartz and galena; and mineralization stage IV with quartz, calcite, and baryte. Tetrahedrite series minerals, such as freibergite, argentotetrahedrite, and tennantite are the main Ag-bearing minerals in the Xinhua deposit. The greatest concentration of silver occurs in phases from mineralization stage II. Microscopic observations reveal close relationship between galena and tetrahedrite series minerals that mostly occur as irregular inclusions within galena. The negative correlation between Cu and Ag in the lattices of tetrahedrite series minerals suggests that Cu sites are occupied by Ag atoms. Zn substitution for Fe in argentotetrahedrite and Cd substitution for Pb in tetrahedrite are also observed. Micro-thermometric data reveal that both homogenization temperatures and calculated salinities of hydrothermal fluids decrease progressively from the early to the later mineralization stages. The metal ions, such as Ag+, Cu+, Pb2+, and Zn2+, are transported as chlorine complex ions in the early mineralization stage and as bisulfide complex ions in the late mineralization stage, caused by changes in oxygen fugacity, temperature, and pH of the hydrothermal fluids. Because of the varying solubility of different metal ions, Pb2+, Zn2+, and Cu2+ ions are initially precipitated as galena, sphalerite, and chalcopyrite, respectively. With

Timing of porphyry (Cu-Mo) and base metal (Zn-Pb-Ag-Cu) mineralisation in a magmatic-hydrothermal system—Morococha district, Peru

NASA Astrophysics Data System (ADS)

Catchpole, Honza; Kouzmanov, Kalin; Bendezú, Aldo; Ovtcharova, Maria; Spikings, Richard; Stein, Holly; Fontboté, Lluís

2015-12-01

The Morococha district in central Peru is characterised by economically important Cordilleran polymetallic (Zn-Pb-Ag-Cu) vein and replacement bodies and the large Toromocho porphyry Cu-Mo deposit in its centre. U-Pb, Re-Os, and 40Ar/39Ar geochronology data for various porphyry-related hydrothermal mineralisation styles record a 3.5-Ma multi-stage history of magmatic-hydrothermal activity in the district. In the late Miocene, three individual magmatic-hydrothermal centres were active: the Codiciada, Toromocho, and Ticlio centres, each separated in time and space. The Codiciada centre is the oldest magmatic-hydrothermal system in the district and consists of a composite porphyry stock associated with anhydrous skarn and quartz-molybdenite veins. The hydrothermal events are recorded by a titanite U-Pb age at 9.3 ± 0.2 Ma and a molybdenite Re-Os age at 9.26 ± 0.03 Ma. These ages are indistinguishable from zircon U-Pb ages for porphyry intrusions of the composite stock and indicate a time span of 0.2 Ma for magmatic-hydrothermal activity. The small Ticlio magmatic-hydrothermal centre in the west of the district has a maximum duration of 0.3 Ma, ranging from porphyry emplacement to porphyry mineralisation at 8.04 ± 0.14 Ma (40Ar/39Ar muscovite cooling age). The Toromocho magmatic-hydrothermal centre has a minimum of five recorded porphyry intrusions that span a total of 1.3 Ma and is responsible for the formation of the giant Toromocho Cu-Mo deposit. At least two hydrothermal pulses are identified. Post-dating a first pulse of molybdenite mineralisation, wide-spread hydrous skarn covers an area of over 6 km2 and is recorded by five 40Ar/39Ar cooling ages at 7.2-6.8 Ma. These ages mark the end of the slowly cooling and long-lived Toromocho magmatic-hydrothermal centre soon after last magmatic activity at 7.26 ± 0.02 Ma. District-wide (50 km2) Cordilleran base metal vein and replacement bodies post-date the youngest recorded porphyry mineralisation event at Toromocho

The spatial and temporal trends of Cd, Cu, Hg, Pb and Zn in Seine River floodplain deposits (1994-2000)

USGS Publications Warehouse

Grosbois, C.; Meybeck, Michel; Horowitz, A.; Ficht, A.

2006-01-01

Fresh floodplain deposits (FD), from 11 key stations, covering the Seine mainstem and its major tributaries (Yonne, Marne and Oise Rivers), were sampled from 1994 to 2000. Background levels for Cd, Cu, Hg, Pb, and Zn were established using prehistoric FD and actual bed sediments collected in small forested sub-basins in the most upstream part of the basin. Throughout the Seine River Basin, FD contain elevated concentrations of Cd, Cu, Hg, Pb and Zn compared to local background values (by factors > twofold). In the Seine River Basin, trace element concentrations display substantial downstream increases as a result of increasing population densities, particularly from Greater Paris (10 million inhabitants), and reach their maxima at the river mouth (Poses). These elevated levels make the Seine one of the most heavily impacted rivers in the world. On the other hand, floodplain-associated trace element levels have declined over the past 7 years. This mirrors results from contemporaneous suspended sediment surveys at the river mouth for the 1984-1999 period. Most of these temporal declines appear to reflect reductions in industrial and domestic solid wastes discharged from the main Parisian sewage plant (Seine Aval). ?? 2005 Elsevier B.V. All rights reserved.

The function of digestive enzymes on Cu, Zn, and Pb release from soil in in vitro digestion tests.

PubMed

Li, Yi; Demisie, Walelign; Zhang, Ming-kui

2013-07-01

The bioaccessibility of soil heavy metals is the solubility of soil heavy metals in synthetic human digestive juice, which is usually determined using in vitro digestion test. To reveal the effects of digestive enzymes on soil heavy metals bioaccessibility, three representative in vitro digestion tests, Simple Bioaccessibility Extraction Test (SBET), Physiologically Based Extraction Test (PBET), and Simple Gastrointestinal Extraction Test (SGET), were chosen. The bioaccessibility of soil Cu, Zn, and Pb in each method were respectively evaluated with and without digestive enzymes, and the differences were compared. The results showed that the effects of digestive enzymes varied with different methods and elements. Because of digestive enzymes addition, the environmental change from acid gastric phase to neutral intestinal phase of PBET did not result in apparently decrease of the bioaccessibility of soil Cu. However, the solubility of soil Zn and Pb were pH-dependent. For SGET, when digestive enzymes were added, its results reflected more variations resulting from soil and element types. The impacts of digestive enzymes on heavy metal dissolution are mostly seen in the intestinal phase. Therefore, digestive enzyme addition is indispensable to the gastrointestinal digestion methods (PBET and SGET), while the pepsin addition is not important for the methods only comprised of gastric digestion (SBET).

Determination and maternal transfer of heavy metals (Cd, Cu, Zn, Pb and Hg) in the Hawksbill sea turtle (Eretmochelys imbricata) from a nesting colony of Qeshm Island, Iran.

PubMed

Ehsanpour, Maryam; Afkhami, Majid; Khoshnood, Reza; Reich, Kimberly J

2014-06-01

This study was conducted to determine trace metal concentrations (Cd, Cu, Zn, Pb and Hg) in blood and three egg fractions from Eretmochelys imbricata nesting on Qeshm Island in Iran. The results showed detectable levels of all analytes in all fractions. Pb and Hg were detectable in the blood and eggs, reflecting a maternal transfer. With the exception of Cu and Pb, analyzed elements in eggs were concentrated in yolk. Only Zn in blood had a significant correlation with the body size and weight (p < 0.01). It appears that Hawksbill sea turtles can regulate Zn concentrations through homeostatic processes to balance metabolic requirements. The relatively low concentrations of metals in blood support the knowledge that E. imbricata feed mainly on the low trophic levels. All essential and non-essential elements were detectable in blood and in eggs of the hawksbill, reflecting a maternal transfer. Consequently, movement patterns, home ranges of foraging grounds, and availability of food could explain variations in trace element concentrations among female turtles.

Removal of Cu, Zn, Pb, and Cr from Yangtze Estuary Using the Phragmites australis Artificial Floating Wetlands

PubMed Central

Zhao, Feng; Yu, Gao; Song, Chao; Geng, Zhi

2017-01-01

Contamination of heavy metals would threaten the water and soil resources; phytoremediation can be potentially used to remediate metal contaminated sites. We constructed the Phragmites australis artificial floating wetlands outside the Qingcaosha Reservoir in the Yangtze Estuary. Water characteristic variables were measured in situ by using YSI Professional Pro Meter. Four heavy metals (copper, zinc, lead, and chromium) in both water and plant tissues were determined. Four heavy metals in estuary water were as follows: 0.03 mg/Kg, 0.016 mg/Kg, 0.0015 mg/Kg, and 0.004 mg/Kg. These heavy metals were largely retained in the belowground tissues of P. australis. The bioaccumulation (BAF) and translation factor (TF) value of four heavy metals were affected by the salinity, temperature, and dissolved oxygen. The highest BAF of each metal calculated was as follows: Cr (0.091 in winter) > Cu (0.054 in autumn) > Pb (0.016 in summer) > Zn (0.011 in summer). Highest root-rhizome TF values were recorded for four metals: 6.450 for Cu in autumn, 2.895 for Zn in summer, 7.031 for Pb in autumn, and 2.012 for Cr in autumn. This indicates that the P. australis AFW has potential to be used to protect the water of Qingcaosha Reservoir from heavy metal contamination. PMID:28717650

Geochemical behavior, environmental availability, and reconstruction of historical trends of Cu, Pb, and Zn in sediment cores of the Cananéia-Iguape coastal system, Southeastern Brazil.

PubMed

Tramonte, Keila Modesto; Figueira, Rubens Cesar Lopes; Majer, Alessandra Pereira; de Lima Ferreira, Paulo Alves; Batista, Miriam Fernanda; Ribeiro, Andreza Portella; de Mahiques, Michel Michaelovitch

2018-02-01

The Cananéia-Iguape system is located in a coastal region of southeastern Brazil, recognized by UNESCO as an Atlantic Forest Biosphere Reserve. This system has suffered substantial environmental impacts due to the opening of an artificial channel and by past intensive mining activities. In this paper was performed the sequential chemical extraction of Cu, Pb, and Zn, on previously described sediment cores, and the statistical treatment of the data, allowing to estimate the remobilization geochemical behavior, the available content and the trend of accumulation between 1926 and 2008. The maximum available level (sum of all mobile fraction) were, in mgkg -1 , 18.74 for Cu, 177.55 for Pb and 123.03 for Zn. Considering its environmental availability, Pb remains a concern in the system. It was possible to recognize the anthropic contribution of Pb, being the mining activities considered the only potential source of this metal in the region. Copyright © 2017 Elsevier Ltd. All rights reserved.

Concentrations of Cd, Cu, Pb and Zn in soft tissue of oyster (Saccostrea cucullata) collected from the Lengeh Port coast, Persian Gulf, Iran: a comparison with the permissible limits for public health.

PubMed

Heidari, Behnam; Riyahi Bakhtiari, Alireza; Shirneshan, Golshan

2013-12-01

This study examines concentrations of Cd, Cu, Pb and Zn in the soft tissue of Saccostrea cucullata in the intertidal zones of Lengeh Port, Persian Gulf, Iran, to survey whether heavy metals are within the acceptable limits for public health? The results revealed that the average metal concentrations (μg/g dry weight) ranged from 10.28 to 12.03 for Cd, 294.10 to 345.80 for Cu, 20.64 to 58.23 for Pb and 735.60 to 760.40 for Zn in the soft tissue of oysters. From the human public health point of view, comparison between the mean concentrations of the metals in the soft tissue of oyster and global guidelines clearly indicates that nearly in all cases concentrations are higher than the permissible amounts for human consumption. In addition, levels of Zn, Pb and Cu were well below their recommended oral maximum residue level (MRLs), whereas levels of Cd were observed two times higher. Copyright © 2013 Elsevier Ltd. All rights reserved.

CORRELATION OF THE PARTITIONING OF DISSOLVED ORGANIC MATTER FRACTIONS WITH THE DESORPTION OF CD, CU, NI, PB AND ZN FROM 18 DUTCH SOILS

EPA Science Inventory

Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was also concentrated onto a macroreticular resin and fractionation into three operationally defined fract...

Geologic, geochemical, and isotopic studies of a carbonate- and siliciclastic-hosted Pb-Zn deposit at Lion Hill, Vermont

USGS Publications Warehouse

Foley, Nora K.; Clark, Sandra H.B.; Woodruff, Laurel G.; Mosier, Elwin L.

1995-01-01

The prospect of an Irish-type sedimentary-exhalative origin for stratabound Pb-Zn deposits of the Paleozoic shelf of North America is of considerable importance to understanding the timing of mineralization relative to platform evolution and for evaluating the mineral resource potential of the region. Our study of the Lion Hill deposit indicates a potential for Irish-type Pb-Zn deposits in platform rocks of western Vermont; however, at Lion Hill they contain enrichments of Pb, Zn, and Cu rather than a Pb, Zn, and Ag association.

Different binding modes of Cu and Pb vs. Cd, Ni, and Zn with the trihydroxamate siderophore desferrioxamine B at seawater ionic strength

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schijf, Johan; Christenson, Emily A.; Potter, Kailee J.

2015-07-01

The solution speciation in seawater of divalent trace metals (Cd, Cu, Ni, Pb, Zn) is dominated by strong, ostensibly metal-specific organic ligands that may play important roles in microbial metal acquisition and/or detoxification processes. We compare the effective stabilities of these metal-organic complexes to the stabilities of their complexes with a model siderophore, desferrioxamine B (DFOB). While metal-DFOB complexation has been studied in various dilute but often moderately coordinating media, for the purpose of this investigation we measured the stability constants in a non-coordinating background electrolyte at seawater ionic strength (0.7 M NaClO4). Potentiometric titrations of single metals (M) weremore » performed in the presence of ligand (L) at different M:L molar ratios, whereupon the stability constants of multiple complexes were simultaneously determined by non-linear regression of the titration curves with FITEQL, using the optimal binding mode for each metal. Cadmium, Ni, and Zn, like trivalent Fe, sequentially form a bi-, tetra-, and hexadentate complex with DFOB as pH increases, consistent with their coordination number of 6 and regular octahedral geometry. Copper has a Jahn-Teller-distorted square-bipyramidal geometry whereas the geometry of Pb is cryptic, involving a range of bond lengths. Supported by a thermodynamic argument, our data suggest that this impedes binding of the third hydroxamate group and that the hexadentate Cu-DFOB and Pb-DFOB complex identified in earlier reports may instead be a deprotonated tetradentate complex. Absence of the hexadentate complex promotes the formation of a dinuclear (bidentate-tetradentate) complex, M2HL2+, albeit not for Pb in 0.7 M NaCl, evidently due to extensive complexation with chloride. Stabilities of the hexadentate Ni-DFOB, Zn-DFOB, and the tetradentate Pb-DFOB complex are nearly equal, yet about 2 orders of magnitude higher and 4 orders of magnitude lower than those of the hexadentate Cd

Differences in the mobility of Cd, Cu, Pb and Zn during composting of two types of household bio-waste collected in four seasons.

PubMed

Hanc, Ales; Szakova, Jirina; Ochecova, Pavla

2014-09-01

The objective of this study was to evaluate the mobility of Cd, Cu, Pb and Zn during 3 different compost aeration rates of household bio-waste, originating in urban settlement (U-bio-waste) and family house buildings (F-bio-waste). The first two weeks, when the thermophilic composting phase became, the highest decline of exchangeable content was recorded. After 12 weeks of composting, lower exchangeable content was found in the case of U-bio-waste composts than F-bio-waste composts, despite higher loss of fresh mass. The order of fractions in both final composts was as follows: residual>oxidizable>reducible>exchangeable. The exchangeable portion of total content in final composts decreased in this order: Zn (17%), Cd (11%), Pb (4%) and Cu (3%). Regarding the low exchangeable content of heavy metals and high-quality organic matter, these types of composts could be used not only as fertilizer, but for remediation of metals contaminated land. Copyright © 2014 Elsevier Ltd. All rights reserved.

Metal accumulation strategies in plants spontaneously inhabiting Zn-Pb waste deposits.

PubMed

Wójcik, Małgorzata; Sugier, Piotr; Siebielec, Grzegorz

2014-07-15

Metal (Zn, Pb, Cd, Cu, Ni, Cr) accumulation in shoots of 38 plant species spontaneously colonizing three Zn-Pb waste deposits in southern Poland was studied in order to find out if the age of the waste (30-130 years) or its type (slag or flotation residues) influence metal content in plants and to identify species potentially suitable for biomonitoring and phytoremediation. The total metal concentrations in the waste upper layers ranged from 7300 to 171,790 mg kg(-1) for Zn, from 1390 to 22,265 mg kg(-1) for Pb, and from 66 to 1,464 mg kg(-1) for Cd, whereas CaCl2-extracted fractions accounted for 0.034-0.11 %, 0.005-0.03 %, and 0.28-0.62 % of total Zn, Pb and Cd concentrations, respectively. The concentrations of Cu, Ni, and Cr in substrates and in plants were low and ranged within the background values. Metal accumulation in plant shoots was poorly correlated with both total and CaCl2-extracted forms of metals in the substrate and was highly variable among species and also specimens of the same species. The highest mean concentrations of Zn, Pb and Cd were found in Anthyllis vulneraria L. (901.5 mg kg(-1)), Echium vulgare L. (116.92 mg kg(-1)), and Hieracium piloselloides Vill. (26.86 mg kg(-1)), respectively. Besides Reseda lutea L., no species appeared to be a good indicator of polymetallic environment pollution based on chemical analysis of shoots; however, metal accumulation in the whole plant communities of a particular contaminated area might be an accurate tool for assessment of metal transfer to vegetation irrespective of the type or age of the waste. All the species studied developed a metal exclusion strategy, thus exhibiting potential for phytostabilization of metalliferous wastelands. Copyright © 2014 Elsevier B.V. All rights reserved.

Geospatial Mapping of Pb, Cr, Cu, Zn, Cd, and Sb in Urban Soil, Cd. Juarez, Chihuahua, Mexico

NASA Astrophysics Data System (ADS)

Amaya, M. A.; Grimida, S. E.; Elkekli, A. R.; Aldouri, R. K.; Benedict, B. A.; Pingitore, N. E., Jr.

2015-12-01

Population-based random stratified sampling of the city of Cd. Juarez, Chihuahua, Mexico provided 500 city blocks for study. We collected soil from the public space (where present) in front of each house on a selected block; equal measured small volumes of these were combined to produce a composite sample for analysis. Such composite samples (1) decrease, by an order of magnitude, laboratory processing and analysis costs, and (2) smooth the data to represent blocks as averages of individual houses. Retention of the unanalyzed samples of the individual houses permits their later analysis should the composites suggest further study of individual houses on an anomalous block. Elemental analysis of 10 mg pressed powders was performed on a Panalytical Epsilon5 EDS-XRF, via 8 secondary targets and 12 USGS and NIST multi-element rock standards. The mean and (range) of concentration for Pb was 43 (13-550) ppm; for Cr, 31 (1.8-76); for Cu, 22 (6-550); for Zn 84 (42-415) ppm; for Cd, 1.9 (0.1-6.2); and for Sb, 5.9 (2.7-29). The old urban core of Cd. Juarez was marked by high levels of Pb, Cr, Cu, and Zn, and, to a smaller degree, of Cd and Sb. This pattern mirrors that of contiguous El Paso, Texas, USA, directly across the narrow Rio Grande. Businesses, industrial facilities, transportation (both railroads and highways), traditional "downtown" shopping, and old residential districts cluster in this urban core. A Pb-Cu-Zn smelter, which operated for more than a century until 1999, is present in the US adjacent to the Rio Grande, about two km away from downtown Cd. Juarez. Thus the city has been subject to both traditional metal sources (e.g., leaded gasoline, highway debris) and smelter emissions. The poplation of Cd. Juarez has exploded in the last few decades to some 1.5 million inhabitants due both to natural growth and in-migration from rural districts for economic opportunity. Most of this growth has been accommodated by radial expansion of the city into the surrounding

Accumulation of Zn, Cd, Cu, and Pb in Chinese cabbage as influenced by climatic conditions under protected cultivation.

PubMed

Moreno, Diego A; Víllora, Gemma; Hernández, Joaquín; Castilla, Nicolás; Romero, Luis

2002-03-27

Accumulation of heavy metals from agricultural soils contaminated by low levels heavy metals has important implications in the understanding of heavy metal contamination in the food chain. Through field experiments (1994-1996), the influence of thermal regime under different treatments on the accumulation of zinc, cadmium, copper, and lead in Chinese cabbage [Brassica pekinensis (Lour) Rupr. cv. Nagaoka 50] grown in a Calcareous Fluvisol (Xerofluvent) in Granada (southern Spain) was examined. Two floating row covers were used: T(1) (perforated polyethylene, 50 microm thick) and T(2) (17 g m(-2) polypropylene nonwoven fleece). An uncovered cultivation (T(0)) served as control. Zn, Cd, Cu, and Pb levels in the whole tops of experimental plants were analyzed. Treatments T(1) and T(2) gave rise to differences in environmental conditions with respect to T(0). The influence of environmental factors manipulated by floating row covers (particularly under T(1)) increased total heavy metal accumulation in the above ground plant biomass with respect to the open-air crop. The total contents of Zn, Cd, Cu, and Pb were 30, 50, 90, and 40% higher in T(1), respectively, than in T(0). This technique could be used in contaminated zones for different plant species because the thermal effect favors the process of phytoextraction and thus reduces the contamination.

Heavy Metals (Cd, Cu, Cr, Pb and Zn) in Meretrix meretrix Roding, Water and Sediments from Estuaries in Sabah, North Borneo

ERIC Educational Resources Information Center

Abdullah, Mohd. Harun; Sidi, Jovita; Aris, Ahmad Zaharin

2007-01-01

Concentrations of heavy metals (Cd, Cu, Cr, Pb and Zn) in tissues of Meretrix meretrix Roding (M. meretrix R.), water and sediments from two estuaries were determined. One estuary is located in an urban area of Kota Kinabalu (Likas estuary) and the other in a rural district of Kota Belud (Kota Belud estuary), where both are in Sabah, North of…

Laser-produced spectra and QED effects for Fe-, Co-, Cu-, and Zn-like ions of Au, Pb, Bi, Th, and U

NASA Technical Reports Server (NTRS)

Seely, J. F.; Ekberg, J. O.; Brown, C. M.; Feldman, U.; Behring, W. E.

1986-01-01

Spectra of very highly charged ions of Au, Pb, Bi, Th, and U have been observed in laser-produced plasmas generated by the OMEGA laser. Line identifications in the region 9-110 A were made for ions in the Fe, Co, Cu, and Zn isoelectronic sequences. Comparison of the measured wavelengths of the Cu-like ions with values calculated with and without QED corrections shows that the inclusion of QED corrections greatly improves the accuracy of the calculated 4s-4p wavelengths. However, significant differences between the observed and calculated values remain.

210Po Activity and concentrations of selected trace elements (As, Cd, Cu, Hg, Pb, Zn) in the muscle tissue of tunas Thunnus albacares and Katsuwonus pelamis from the Eastern Pacific Ocean.

PubMed

Ruelas-Inzunza, Jorge; Soto-Jiménez, Martín Federico; Ruiz-Fernández, Ana Carolina; Bojórquez-Leyva, Humberto; Pérez-Bernal, Hascibe; Páez-Osuna, Federico

2012-12-01

Daily mineral intake (DMI) of Cu and Zn, percentage weekly intake (PWI) of As, Cd, Hg, Pb, and doses of (210)Po were estimated by using their elemental concentration in muscle of two tuna species and the average tuna consumption in Mexico. Skipjack tuna Katsuwonus pelamis had significantly (p < 0.05) higher levels of As (1.38 μg g(-1) dw) and Cu (1.85 μg g(-1) dw) than yellowfin tuna Thunnus albacares, whereas Pb concentrations (0.18 μg g(-1) dw) were significantly (p < 0.05) higher in T. albacares. The sequence of elemental concentrations in both species was Zn > Cu > As > Hg > Pb > Cd. In T. albacares, concentrations of Cd and Pb in muscle tissue were positively correlated (p < 0.05) with weight of specimens, while Cu was negatively correlated. DMI values were below 10 %. PWI figures (<2 %) are not potentially harmful to human health. (210)Po concentration in T. albacares and K. pelamis accounts for 13.5 to 89.7 % of the median individual annual dose (7.1 μSv) from consumption of marine fish and shellfish for the world population.

Predicting As, Cd, Cu, Pb and Zn levels in grasses (Agrostis sp. and Poa sp.) and stinging nettle (Urtica dioica) applying soil-plant transfer models.

PubMed

Boshoff, Magdalena; De Jonge, Maarten; Scheifler, Renaud; Bervoets, Lieven

2014-09-15

The aim of this study was to derive regression-based soil-plant models to predict and compare metal(loid) (i.e. As, Cd, Cu, Pb and Zn) concentrations in plants (grass Agrostis sp./Poa sp. and nettle Urtica dioica L.) among sites with a wide range of metal pollution and a wide variation in soil properties. Regression models were based on the pseudo total (aqua-regia) and exchangeable (0.01 M CaCl2) soil metal concentrations. Plant metal concentrations were best explained by the pseudo total soil metal concentrations in combination with soil properties. The most important soil property that influenced U. dioica metal concentrations was the clay content, while for grass organic matter (OM) and pH affected the As (OM) and Cu and Zn (pH). In this study multiple linear regression models proved functional in predicting metal accumulation in plants on a regional scale. With the proposed models based on the pseudo total metal concentration, the percentage of variation explained for the metals As, Cd, Cu, Pb and Zn were 0.56%, 0.47%, 0.59%, 0.61%, 0.30% in nettle and 0.46%, 0.38%, 0.27%, 0.50%, 0.28% in grass. Copyright © 2014 Elsevier B.V. All rights reserved.

Soil solution dynamics of Cu and Zn in a Cu- and Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction.

PubMed

Luo, Y M; Yan, W D; Christie, P

2001-01-01

A pot experiment was conducted to study soil solution dynamics of Cu and Zn in a Cu/Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction. A slightly acid sandy loam was amended with Cu and Zn (as nitrates) either singly or in combination (100 mg Cu and 150 mg Zn kg(-1) soil) and was then gamma-irradiated (10 kGy). Unamended and unirradiated controls were included, and spring barley (Hordeum vulgare L. cv. Forrester) was grown for 50 days. Soil solution samples obtained using soil moisture samplers immediately before transplantation and every ten days thereafter were used directly for determination of Cu, Zn, pH and absorbance at 360 nm (A360). Cu and Zn concentrations in the solution of metal-polluted soil changed with time and were affected by gamma-irradiation and metal interaction. gamma-Irradiation raised soil solution Cu substantially but generally decreased soil solution Zn. These trends were consistent with increased dissolved organic matter (A360) and solution pH after gamma-irradiation. Combined addition of Cu and Zn usually gave higher soil solution concentrations of Cu or Zn compared with single addition of Cu or Zn in gamma-irradiated and non-irradiated soils, indicating an interaction between Cu and Zn. Cu would have been organically complexed and consequently maintained a relatively high concentration in the soil solution under higher pH conditions. Zn tends to occur mainly as free ion forms in the soil solution and is therefore sensitive to changes in pH. The extent to which gamma-irradiation and metal interaction affected solubility and bioavailability of Cu and Zn was a function of time during plant growth. Studies on soil solution metal dynamics provide very useful information for understanding metal mobility and bioavailability.

Effects of three low-molecular-weight organic acids (LMWOAs) and pH on the mobilization of arsenic and heavy metals (Cu, Pb, and Zn) from mine tailings.

PubMed

Wang, Suiling; Mulligan, Catherine N

2013-02-01

Natural organic acids may play an important role in influencing the mobility of toxic contaminants in the environment. The mobilization of arsenic (As) and heavy metals from an oxidized Pb-Zn mine tailings sample in the presence of three low-molecular-weight organic acids, aspartic acid, cysteine, and succinic acid, was investigated at a mass ratio of 10 mg organic additive/g mine tailings in this study. The effect of pH was also evaluated. The mine tailings sample, containing elevated levels of As (2,180 mg/kg), copper (Cu, 1,100 mg/kg), lead (Pb, 12,860 mg/kg), and zinc (Zn, 5,075 mg/kg), was collected from Bathurst, New Brunswick, Canada. It was found that the organic additives inhibited As and heavy metal mobilization under acidic conditions (at pH 3 or 5), but enhanced it under neutral to alkaline conditions (at pH above 7) through forming aqueous organic complexes. At pH 11, As, Cu, Pb, and Zn were mobilized mostly by the organic additives, 45, 46, 1,660, and 128 mg/kg by aspartic acid, 31, 28, 1,040, and 112 mg/kg by succinic acid, and 53, 38, 2,020, and 150 mg/kg by cysteine, respectively, whereas those by distilled water were 6, 16, 260, and 52 mg/kg, respectively. It was also found that the mobilization of As and the heavy metals was closely correlated, and both were closely correlated to Fe mobilization. Arsenic mobilization by the three LMWOAs was found to be consistent with the order of the stability of Fe-, Cu-, Pb-, and Zn-organic ligand complexes. The organic acids might be used potentially in the natural attenuation and remediation of As and heavy metal-contaminated sites.

Distribution and speciation of metals (Cu, Zn, Cd, and Pb) in agricultural and non-agricultural soils near a stream upriver from the Pearl River, China.

PubMed

Yang, Silin; Zhou, Dequn; Yu, Huayong; Wei, Rong; Pan, Bo

2013-06-01

The distribution and chemical speciation of typical metals (Cu, Zn, Cd and Pb) in agricultural and non-agricultural soils were investigated in the area of Nanpan River, upstream of the Pearl River. The investigated four metals showed higher concentrations in agricultural soils than in non-agricultural soils, and the site located in factory district contained metals much higher than the other sampling sites. These observations suggested that human activities, such as water irrigation, fertilizer and pesticide applications might have a major impact on the distribution of metals. Metal speciation analysis presented that Cu, Zn and Cd were dominated by the residual fraction, while Pb was dominated by the reducible fraction. Because of the low mobility of the metals in the investigated area, no remarkable difference could be observed between upstream and downstream separated by the factory site. Copyright © 2013 Elsevier Ltd. All rights reserved.

Simultaneous removal of aqueous Zn2+, Cu2+, Cd2+, and Pb2+ by zeolites synthesized from low-calcium and high-calcium fly ash.

PubMed

Ji, X D; Ma, Y Y; Peng, S H; Gong, Y Y; Zhang, F

2017-10-01

In this study, zeolites were synthesized from low-calcium (LCZ) and high-calcium (HCZ) fly ash, respectively. Subsequently, the zeolites were tested for their removal effectiveness for four aqueous cations, namely, Zn 2+ , Cu 2+ , Cd 2+ , and Pb 2+ , as a function of contact time, pH value, adsorbent dosage, and initial concentration of heavy metals. Both zeolites were characterized by X-ray diffraction, X-ray fluorescence spectrometry, scanning electron microscopy, specific surface area, and cation exchange capacity. The results show that HCZ mainly consists of an unnamed zeolite (Na 6 [AlSiO 4 ] 6 ·4H 2 O), whereas LCZ mainly consists of faujasite-type zeolite. The optimum sorption conditions were pH = 6.0; adsorbent dosage = 1.0 g·L -1 ; temperature = 25 °C; contact time = 100 min; and initial heavy metal concentration = 100 mg·L -1 . The sorption kinetics of the four aqueous cations on both LCZ and HCZ followed the pseudo-second-order kinetic model, and the sorption isotherm data fitted well with the Langmuir isotherm model. For LCZ, the maximum adsorption capacities of Zn 2+ , Cu 2+ , Cd 2+ , and Pb 2+ were 155.76, 197.86, 123.76, and 186.22 mg·g -1 , respectively. For HCZ, the values were 154.08, 183.15, 118.91, and 191.94 mg·g -1 , respectively. The zeolites were regenerated by NaCl solution (1 mol·L -1 ) and showed high removal efficiency. In conclusion, zeolites produced by fly ash are promising materials for removing Zn 2+ , Cu 2+ , Cd 2+ , and Pb 2+ from wastewater.

Geochemistry of the Patricia Zn-Pb-Ag Deposit (paguanta, NE Chile)

NASA Astrophysics Data System (ADS)

Chinchilla Benavides, D.; Merinero Palomares, R.; Piña García, R.; Ortega Menor, L.; Lunar Hernández, R.

2013-12-01

The Patricia Zn-Pb-Ag ore deposit is located within the Paguanta mining project, situated at the northern end of the Andean Oligocene Porphyry Copper Belt of Chile. The sulfide mineralization occurs as W-E oriented veins hosted in volcanic rocks, mainly andesite (pyroclastic, ash and lavas), of Upper Cretaceous to Middle Tertiary age. The ore mineralogy (obtained by EMPA analyses) comprises in order of abundance, pyrite, sphalerite (5.5 - 10.89 wt % Fe, 9.8-19 % molar FeS and 0.52 wt % Cd), galena, arsenopyrite, chalcopyrite and Ag-bearing sulfosalts. The veins show a zoned and banded internal structure with pyrite at the edges and sphalerite in the center. The Ag occurs mostly as Ag-Cu-Sb sulfosalts, in order of abundance: series freibergite - argentotennantite -polybasite and stephanite. Other minor Ag phases such as argentite, pyrargirite and diaphorite were also identified. These Ag phases are typically associated with the base-metal sulfides. Freibergite occurs filling voids within sphalerite, chalcopyrite and at the contact between sphalerite and galena. Polybasite, stephanite, pyrargirite and argentite are mostly in close association with freibergite. In the case of diaphorite, it commonly occurs filling voids between galena crystals or as inclusions within galena. Some minor Ag-bearing sulfosalts are also identified between pyrite crystals. The alteration minerals are dominated by chlorite, illite and kaolinite. The gangue minerals consist of quartz and carbonates identified by XRD as kutnahorite. We obtained linear correlation statistically significant only for Ag, As Au, Cd, Cu, Pb, Sb and Zn and therefore we generated an enhanced scatter plot matrix of these elements. Bulk rock analyses (ICP/MS and XRF) of drill cores show that Ag is strongly and positively correlated with Pb and As, moderately with Cd, Sb, Au and Zn and weakly with Cu, while Au is moderately and positively correlated with Ag, As, Cd, Sb and Zn and weakly with Cu and Pb. These results

Study of the ambient air metallic elements Cr, Cu, Zn, Cd and Pb at HAF sampling sites.

PubMed

Fang, Guor-Cheng; Kuo, Yu-Chen; Zhuang, Yuan-Jie; Tsai, Kai-Hsiang; Huang, Wen-Chuan

2017-08-01

This study characterized diurnal variations in the compositions of total suspended particulates (TSP) and dry deposits of particulates from ambient air, and the metallic elements that are contained in them at harbor, airport and farmland (HAF) sampling sites from August, 2013 to July, 2014. Two-way ANOVA of the amounts of metallic elements in the TSP and dry deposits was carried out in all four seasons at the HAF sampling sites. The metallic elements Cr and Cu originated in local emission sources at the airport. Metallic elements Zn and Pb originated in local emission sources at the harbor. Finally, metallic element Cd originated in local emissions form farmland. The following results were also obtained. (1) The metallic composition of the TSP differed significantly from that of the dry deposits in all four seasons at the harbor and farmland sampling sites, but not at the airport sampling site. (2) High correlations coefficients were found between the amounts of metallic elements Cr and Cu in the TSP and those in the dry deposits at the airport sampling site. (3) Pb was present in the TSP and the dry deposits at the harbor sampling site.

Electrodeposition of Zn and Cu-Zn alloy from ZnO/CuO precursors in deep eutectic solvent

NASA Astrophysics Data System (ADS)

Xie, Xueliang; Zou, Xingli; Lu, Xionggang; Lu, Changyuan; Cheng, Hongwei; Xu, Qian; Zhou, Zhongfu

2016-11-01

The electrodeposition of Zn and Cu-Zn alloy has been investigated in choline chloride (ChCl)/urea (1:2 molar ratio) based deep eutectic solvent (DES). Cyclic voltammetry study demonstrates that the reduction of Zn(II) to Zn is a diffusion-controlled quasi-reversible, one-step, two electrons transfer process. Chronoamperometric investigation indicates that the electrodeposition of Zn on a Cu electrode typically involves three-dimensional instantaneous nucleation with diffusion-controlled growth process. Micro/nanostructured Zn films can be obtained by controlling the electrodeposition potential and temperature. The electrodeposited Zn crystals preferentially orient parallel to the (101) plane. The Zn films electrodeposited under more positive potentials and low temperatures exhibit improved corrosion resistance in 3 wt% NaCl solution. In addition, Cu-Zn alloy films have also been electrodeposited directly from CuO-ZnO precursors in ChCl/urea-based DES. The XRD analysis indicates that the phase composition of the electrodeposited Cu-Zn alloy depends on the electrodeposition potential.

Simultaneous determination of suspended particulate trace metals (Co, Ni, Cu, Zn, Cd and Pb) in seawater with small volume filtration assisted by microwave digestion and flow injection inductively coupled plasma mass spectrometer.

PubMed

Nakatsuka, Seiji; Okamura, Kei; Norisuye, Kazuhiro; Sohrin, Yoshiki

2007-06-26

A new technique for the determination of suspended particulate trace metals (P-metals >0.2 microm), such as Co, Ni, Cu, Zn, Cd and Pb, in open ocean seawater has been developed by using microwave digestion coupled with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Suspended particulate matter (SPM) was collected from 500 mL of seawater on a Nuclepore filter (0.2 microm) using a closed filtration system. Both the SPM and filter were completely dissolved by microwave digestion. Reagents for the digestion were evaporated using a clean evaporation system, and the metals were redissolved in 0.8 M HNO3. The solution was diluted with buffer solution to give pH 5.0 and the metals were determined by FI-ICP-MS using a chelating adsorbent of 8-hydroxyquinoline immobilized on fluorinated metal alkoxide glass (MAF-8HQ). The procedure blanks with a filter were found to be 0.048+/-0.008, 10.3+/-0.3, 0.27+/-0.05, 3.3+/-1.8, 0.02+/-0.03 and 0.85+/-0.09 ng L(-1) for Co, Ni, Cu, Zn, Cd and Pb, respectively (n=14). Detection limits defined as 3 times the standard deviation of the blanks were 0.023, 0.90, 0.14, 5.3, 0.078 and 0.28 ng L(-1) for Co, Ni, Cu, Zn, Cd and Pb, respectively. Accuracy was evaluated using certified reference materials of chlorella (NES CRM No. 3) and marine sediment (HISS-1). The method was applied to the determination of vertical distributions for P-Co, Ni, Cu, Zn, Cd and Pb in the Western North Pacific.

Soil Cd, Cr, Cu, Ni, Pb and Zn sorption and retention models using SVM: Variable selection and competitive model.

PubMed

González Costa, J J; Reigosa, M J; Matías, J M; Covelo, E F

2017-09-01

The aim of this study was to model the sorption and retention of Cd, Cu, Ni, Pb and Zn in soils. To that extent, the sorption and retention of these metals were studied and the soil characterization was performed separately. Multiple stepwise regression was used to produce multivariate models with linear techniques and with support vector machines, all of which included 15 explanatory variables characterizing soils. When the R-squared values are represented, two different groups are noticed. Cr, Cu and Pb sorption and retention show a higher R-squared; the most explanatory variables being humified organic matter, Al oxides and, in some cases, cation-exchange capacity (CEC). The other group of metals (Cd, Ni and Zn) shows a lower R-squared, and clays are the most explanatory variables, including a percentage of vermiculite and slime. In some cases, quartz, plagioclase or hematite percentages also show some explanatory capacity. Support Vector Machine (SVM) regression shows that the different models are not as regular as in multiple regression in terms of number of variables, the regression for nickel adsorption being the one with the highest number of variables in its optimal model. On the other hand, there are cases where the most explanatory variables are the same for two metals, as it happens with Cd and Cr adsorption. A similar adsorption mechanism is thus postulated. These patterns of the introduction of variables in the model allow us to create explainability sequences. Those which are the most similar to the selectivity sequences obtained by Covelo (2005) are Mn oxides in multiple regression and change capacity in SVM. Among all the variables, the only one that is explanatory for all the metals after applying the maximum parsimony principle is the percentage of sand in the retention process. In the competitive model arising from the aforementioned sequences, the most intense competitiveness for the adsorption and retention of different metals appears between

Study of Zn-Pb ore tailings and their potential in cement technology

NASA Astrophysics Data System (ADS)

Nouairi, J.; Hajjaji, W.; Costa, C. S.; Senff, L.; Patinha, C.; Ferreira da Silva, E.; Labrincha, J. A.; Rocha, F.; Medhioub, M.

2018-03-01

This paper describes the synthesis of sulfobelite clinkers incorporating mining rejects. The targeted Zn-Pb tailing wastes generated in the diapiric zone (NW Tunisia) were tested in clinker/cement compositions to ensure the inertization of existing hazardous heavy metals. Mineralogical composition of the two selected samples revealed calcite, dolomite, quartz, kaolinite, galena, pyrite and gypsum as crystalline phases. Vertical distributions of dominant heavy metals (Pb, Zn and Cu) in soil profiles show enrichment in the surface layers and decrease towards the depth. In sintered clinkers powders, the presence of the targeted crystalline phases (trialuminate sulphate (C4A3Š), belite (C2S), and ferrite (C4AF)) are in the predicted desirable amounts. Heat flow generated during the hydration of different cement pastes showed a slower reaction for clinkers with higher amounts of C4A3Š or constituted by coarser particles. After 28 days curing, the best mechanical resistance (24.34 MPa under compression) was obtained for the clinker calcined at 1350 °C and showing a suitable particle size distribution. Concerning heavy metals, immobilisation of 75-85% of Pb, Zn and Cu was assessed in the mortars formulated with the produced clinker/cement, posing no hazardous risks to the environment.

Geology of the Göçükdibi Cu-Pb-Zn Mineralization, Gökçedoǧan, Çorum (Turkey): Preliminary Findings on Its Formation

NASA Astrophysics Data System (ADS)

Yalçin, Cihan; Hanilçi, Nurullah; Kumral, Mustafa; Abdelnasser, Amr

2016-04-01

Göçükdibi Cu-Pb-Zn mineralization is located 3 km north west of Gökçedoǧan village where is 30 km east of the Kargı, Çorum. The geology of the mineralization area is represented by Mesozoic and Upper Pliocene lithostratigraphic units in different origin. These units with respect to their structural locations have identified as autochthonous and allachtonous. The autochthonous units which are the basement of the region are represented by Bekirli Metamorphites (Triassic-Liassic) and Beşpınar formation (Upper Cretaceous-Lower Eocene) which overlies the Bekirli Metamorphites as angular discordance. The allachtonous units are represented by Saraycık formation belongs to Kargı Ophioltic Melange, and located on the autochthonous units as tectonically. These allocthonous units are the product of the Neotethyan Ocean. The autochthonous and allachtonous units are overlaid by Upper Pliocene Ilgaz Formation and Plio-Quaternary stream sediments. The Cu-Pb-Zn mineralization is located in northwest of the Gökçedoǧan village within the Bekirli Metamorphites. The ore zone has N80E direction, 5 m wide and 120 m in length. The mineralizations which follow NE-SW trending structural line occurred as alternation with quartz-chlorite schists of the Bekirli Metamorphites. The mineralization is generally concordant to the foliation of schist's and also occurred as disseminated in the wall rocks. The ore paragenesis comprises with pyrite, chalcopyrite, sphalerite and galenit as the main sulphide minerals, and the malachite, azurite and limonite as the production of the oxidation. Preliminary data such as relationship between the ore and host rock, inner-structure of the ore and indicate that the Gökçedoǧan Cu-Pb-Zn mineralization was likely to have originated syngenetic. In addition, the geochemical behaviour of rare earth elements (REE) of the altered and mineralized samples collected from the alteration zone show that light REE enrichment with fair depletion of heavy REE

Importance of lithology in defining natural background concentrations of Cr, Cu, Ni, Pb and Zn in sedimentary soils, northeastern Brazil.

PubMed

Gloaguen, Thomas Vincent; Passe, José João

2017-11-01

The sedimentary basins of Recôncavo and Tucano, Bahia, represent the most important Brazilian Phanerozoic continental basin system, formed during fracturing of Gondwana. The northern basin of Tucano has a semiarid climate (Bsh) while the southern basin of Recôncavo has a tropical rainforest climate (Af). The aim of this study was to determine the distribution of trace metals in soils derived from various sedimentary rocks and climates. Soils were collected at 30 sites in 5 geological units at 0-20 cm and 60-80 cm deep under native vegetation. Physical and chemical attributes (particle size distribution, pH, Al, exchangeable bases, organic matter) were determined, as well as the pseudo-total concentrations (EPA 3050 b) and the total concentrations (X-ray fluorescence) of Cr, Cu, Ni, Pb and Zn. The concentrations of metals were overall correlated to soil texture, according to lithologic origin. Shales resulted in Vertisols 30.4 (Zn), 27.2 (Ni), 16.9 (Cu), 7.5 (Cr) and 2.5 (Pb) times more concentrated than Arenosols derived from the sandstones. High Cr and Ni values in clay soils from shales were attributed to diffuse contamination by erosion of mafic rocks of the Greenstone Belt River Itapicuru (from 3 km northwest of the study area) during the late Jurassic. Tropical rainforest climate resulted in a slight enrichment of Pb and Cr, and Ni had the higher mobility during soil formation (enrichment factor up to 6.01). In conclusion, the geological environment is a much more controlling factor than pedogenesis in the concentration of metals in sedimentary soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

Using isotopic dilution to assess chemical extraction of labile Ni, Cu, Zn, Cd and Pb in soils.

PubMed

Garforth, J M; Bailey, E H; Tye, A M; Young, S D; Lofts, S

2016-07-01

Chemical extractants used to measure labile soil metal must ideally select for and solubilise the labile fraction, with minimal solubilisation of non-labile metal. We assessed four extractants (0.43 M HNO3, 0.43 M CH3COOH, 0.05 M Na2H2EDTA and 1 M CaCl2) against these requirements. For soils contaminated by contrasting sources, we compared isotopically exchangeable Ni, Cu, Zn, Cd and Pb (EValue, mg kg(-1)), with the concentrations of metal solubilised by the chemical extractants (MExt, mg kg(-1)). Crucially, we also determined isotopically exchangeable metal in the soil-extractant systems (EExt, mg kg(-1)). Thus 'EExt - EValue' quantifies the concentration of mobilised non-labile metal, while 'EExt - MExt' represents adsorbed labile metal in the presence of the extractant. Extraction with CaCl2 consistently underestimated EValue for Ni, Cu, Zn and Pb, while providing a reasonable estimate of EValue for Cd. In contrast, extraction with HNO3 both consistently mobilised non-labile metal and overestimated the EValue. Extraction with CH3COOH appeared to provide a good estimate of EValue for Cd; however, this was the net outcome of incomplete solubilisation of labile metal, and concurrent mobilisation of non-labile metal by the extractant (MExtEValue). The Na2H2EDTA extractant mobilised some non-labile metal in three of the four soils, but consistently solubilised the entire labile fraction for all soil-metal combinations (MExt ≈ EExt). Comparison of EValue, MExt and EExt provides a rigorous means of assessing the underlying action of soil chemical extraction methods and could be used to refine long-standing soil extraction methodologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Classification of Broken Hill-Type Pb-Zn-Ag Deposits: A Refinement

NASA Astrophysics Data System (ADS)

Spry, P. G.; Teale, G. S.; Steadman, J. A.

2009-05-01

Broken Hill Hill-type Pb-Zn-Ag (BHT) deposits constitute some of the largest ore deposits in the world. The Broken Hill deposit is the largest accumulation of Pb, Zn, and Ag on Earth and the Cannington deposit is currently the largest silver deposit. Characteristic features of BHT deposits include: 1. high Pb+Zn+Ag values with Pb > Zn; 2. Metamorphism to amphibolite-granulite facies; 3. Paleo-to Mesoprotoerozoic clastic metasedimentary host rocks; 4. Sulfides that are spatially associated with bimodal (felsic and mafic) volcanic rocks, and stratabound gahnite- and garnet-bearing rocks and iron formations, 5. Stacked orebodies with characteristic Pb:Zn:Ag ratios and skarn-like Fe-Mn-Ca-F gangue assemblages, and the presence of Cu, Au, Bi, As, and Sb; and 6. Sulfur-poor assemblages. Broken Hill (Australia) has a prominent footwall feeder zone whereas other BHT deposits have less obvious alteration zones (footwall garnet spotting and stratabound alteration haloes). Deposits previously regarded in the literature as BHT deposits are Broken Hill, Cannington, Oonagalabie, Menninie Dam, and Pegmont (Australia), Broken Hill, Swartberg, Big Syncline, and Gamsberg (South Africa), Zinkgruvan (Sweden), Sullivan, Cottonbelt, and Foster River (Canada), and Boquira (Brazil). Of these deposits, only the Broken Hill (Australia, South Africa), Pinnacles, Cannington, Pegmont, and Swartberg deposits are BHT deposits. Another BHT deposit includes the Green Parrot deposit, Jervois Ranges (Northern Territory). The Foster River, Gamsberg, and Sullivan deposits are considered to be "SEDEX deposits with BHT affinities", and the Oonagalabie, Green Mountain (Colorado), and Zinkgruvan are "VMS deposits with BHT affinities". In the Broken Hill area (Australia), Corruga-type Pb-Zn-Ag deposits occur in calc-silicate rocks and possess some BHT characteristics; the Big Syncline, Cottonbelt, Menninie Dam, and Saxberget deposits are Corruga-type deposits. SEDEX deposits with BHT affinities, VMS

Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Nicol, S.; Hayes, P. C.; Jak, E.

2018-03-01

Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO2) and (b) cuprite (Cu2O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-"CuO0.5"-SiO2 plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.

Initiation of soil formation in weathered sulfidic Cu-Pb-Zn tailings under subtropical and semi-arid climatic conditions.

PubMed

You, Fang; Dalal, Ram; Huang, Longbin

2018-08-01

Field evidence has been scarce about soil (or technosol) formation and direct phytostabilization of base metal mine tailings under field conditions. The present study evaluated key attributes of soil formation in weathered and neutral Cu-Pb-Zn tailings subject to organic amendment (WC: woodchips) and colonization of pioneer native plant species (mixed native woody and grass plant species) in a 2.5-year field trial under subtropical and semi-arid climatic conditions. Key soil indicators of engineered soil formation process were characterized, including organic carbon fractions, aggregation, microbial community and key enzymatic activities. The majority (64-87%) of the OC was stabilized in microaggregate or organo-mineral complexes in the amended tailings. The levels of OC and water soluble OC were elevated by 2-3 folds across the treatments, with the highest level in the treatment of WC and plant colonization (WC+P). Specifically, the WC+P treatment increased the proportion of water stable macroaggregates. Plants further contributed to the N rich organic matter in the tailings, favouring organo-mineral interactions and organic stabilization. Besides, the plants played a major role in boosting microbial biomass and activities in the treated tailings. WC and plants enhanced the contents of organic carbon (OC) associated with aggregates (e.g., physically protected OC), formation of water-stable aggregates (e.g., micro and macroaggregates), chemical buffering capacity (e.g., cation exchange capacity). Microbial community and enzymatic activities were also stimulated in the amended tailings. The present results showed that the formation of functional technosol was initiated in the eco-engineered and weathered Cu-Pb-Zn tailings under field conditions for direct phytostabilization. Copyright © 2018 Elsevier Ltd. All rights reserved.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties

NASA Astrophysics Data System (ADS)

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-01

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications

Ages and sources of components of Zn-Pb, Cu, precious metal, and platinum group element deposits in the goodsprings district, Clark County, Nevada

USGS Publications Warehouse

Vikre, Peter G.; Browne, Quentin J.; Fleck, Robert J.; Hofstra, Albert H.; Wooden, Joseph L.

2011-01-01

The Goodsprings district, Clark County, Nevada, includes zinc-dominant carbonate replacement deposits of probable late Paleozoic age, and lead-dominant carbonate replacement deposits, copper ± precious metal-platinum group element (PGE) deposits, and gold ± silver deposits that are spatially associated with Late Triassic porphyritic intrusions. The district encompasses ~500 km2 although the distribution of all deposits has been laterally condensed by late Mesozoic crustal contraction. Zinc, Pb, and Cu production from about 90 deposits was ~160,000 metric tons (t) (Zn > Pb >> Cu), 2.1 million ounces (Moz) Ag, 0.09 Moz Au, and small amounts of PGEs—Co, V, Hg, Sb, Ni, Mo, Mn, Ir, and U—were also recovered.Zinc-dominant carbonate replacement deposits (Zn > Pb; Ag ± Cu) resemble Mississippi Valley Type (MVT) Zn-Pb deposits in that they occur in karst and fault breccias in Mississippian limestone where the southern margin of the regional late Paleozoic foreland basin adjoins Proterozoic crystalline rocks of the craton. They consist of calcite, dolomite, sphalerite, and galena with variably positive S isotope compositions (δ34S values range from 2.5–13‰), and highly radiogenic Pb isotope compositions (206Pb/204Pb >19), typical of MVT deposits above crystalline Precambrian basement. These deposits may have formed when southward flow of saline fluids, derived from basinal and older sedimentary rocks, encountered thinner strata and pinch-outs against the craton, forcing fluid mixing and mineral precipitation in karst and fault breccias. Lead-dominant carbonate replacement deposits (Pb > Zn, Ag ± Cu ± Au) occur among other deposit types, often near porphyritic intrusions. They generally contain higher concentrations of precious metals than zinc-dominant deposits and relatively abundant iron oxides after pyrite. They share characteristics with copper ± precious metal-PGE and gold ± silver deposits including fine-grained quartz replacement of carbonate minerals

Soil heavy metal pollution and risk assessment associated with the Zn-Pb mining region in Yunnan, Southwest China.

PubMed

Cheng, Xianfeng; Danek, Tomas; Drozdova, Jarmila; Huang, Qianrui; Qi, Wufu; Zou, Liling; Yang, Shuran; Zhao, Xinliang; Xiang, Yungang

2018-03-07

The environmental assessment and identification of sources of heavy metals in Zn-Pb ore deposits are important steps for the effective prevention of subsequent contamination and for the development of corrective measures. The concentrations of eight heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) in soils from 40 sampling points around the Jinding Zn-Pb mine in Yunnan, China, were analyzed. An environmental quality assessment of the obtained data was performed using five different contamination and pollution indexes. Statistical analyses were performed to identify the relations among the heavy metals and the pH in soils and possible sources of pollution. The concentrations of As, Cd, Pb, and Zn were extremely high, and 23, 95, 25, and 35% of the samples, respectively, exceeded the heavy metal limits set in the Chinese Environmental Quality Standard for Soils (GB15618-1995, grade III). According to the contamination and pollution indexes, environmental risks in the area are high or extremely high. The highest risk is represented by Cd contamination, the median concentration of which exceeds the GB15618-1995 limit. Based on the combination of statistical analyses and geostatistical mapping, we identified three groups of heavy metals that originate from different sources. The main sources of As, Cd, Pb, Zn, and Cu are mining activities, airborne particulates from smelters, and the weathering of tailings. The main sources of Hg are dust fallout and gaseous emissions from smelters and tailing dams. Cr and Ni originate from lithogenic sources.

Photoluminescence study of ZnS and ZnS:Pb nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Virpal,, E-mail: virpalsharma.sharma@gmail.com; Hastir, Anita; Kaur, Jasmeet

2015-05-15

Photoluminescence (PL) study of pure and 5wt. % lead doped ZnS prepared by co-precipitation method was conducted at room temperature. The prepared nanoparticles were characterized by X-ray Diffraction (XRD), UV-Visible (UV-Vis) spectrophotometer, Photoluminescence (PL) and Raman spectroscopy. XRD patterns confirm cubic structure of ZnS and PbS in doped sample. The band gap energy value increased in case of Pb doped ZnS nanoparticles. The PL spectrum of pure ZnS was de-convoluted into two peaks centered at 399nm and 441nm which were attributed to defect states of ZnS. In doped sample, a shoulder peak at 389nm and a broad peak centered atmore » 505nm were observed. This broad green emission peak originated due to Pb activated ZnS states.« less

The Transfiguration continental red-bed Cu-Pb-Zn-Ag deposit, Quebec Appalachians, Canada

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Beaudoin, Georges; Taylor, Bruce E.

2009-04-01

The Transfiguration Cu-Pb-Zn-Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from -7.5‰ to -1.1‰ δ13C and from 14.7‰ to 21.3‰ δ18O. The negative δ13C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from -19‰ to 25‰ δ34S, as measured on mineral concentrates by a conventional SO2 technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ34S values, from -21‰ to 25‰. Negative and positive δ34S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ34S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised

Yield strength of Cu and an engineered material of Cu with 1% Pb

NASA Astrophysics Data System (ADS)

Buttler, William; Gray, George, III; Fensin, Saryu; Grover, Mike; Stevens, Gerald; Stone, Joseph; Turley, William

2015-06-01

To study the effects of engineered elastic-plastic yield on the mass-ejection from shocked materials we fielded explosively driven Cu and CuPb experiments. The Cu and CuPb experiments fielded fully annealed disks in contact with PBX 9501; the CuPb was extruded with 1% Pb that aggregates at the Cu grain boundaries. The elastic-plastic yield strength is explored as a difference of ejecta production of CuPb versus Cu, where the ejecta production of solid materials ties directly to the surface perturbation geometries of wavelengths (fixed at 65 μm) and amplitudes (which were varied). We observed that the Cu performs as expected, with ejecta turning on at the previously observed yield threshold, but the CuPb ejects mass in much larger quantities, at much lower wavenumber (k = 2 π/ λ) amplitude (h) products (kh), implying a reduced elastic-plastic yield stress of the engineered material, CuPb.

Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties.

PubMed

Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

2016-06-02

Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.

Spatial distribution and risk assessment of heavy metals in soil near a Pb/Zn smelter in Feng County, China.

PubMed

Shen, Feng; Liao, Renmei; Ali, Amjad; Mahar, Amanullah; Guo, Di; Li, Ronghua; Xining, Sun; Awasthi, Mukesh Kumar; Wang, Quan; Zhang, Zengqiang

2017-05-01

A large scale survey and a small scale continuous monitoring was conducted to evaluate the impact of Pb/Zn smelting on soil heavy metals (HMs) accumulation and potential ecological risk in Feng County, Shaanxi province of China. Soil parameters including pH, texture, CEC, spatial and temporal distribution of HMs (Cd, Cu, Ni, Pb and Zn), and BCR fractionation were monitored accordingly. The results showed the topsoil in the proximity of smelter, especially the smelter area and county seat, were highly polluted by HMs in contrast to the river basins. Fractionation of Cd and Zn in soil samples revealed higher proportion of mobile fractions than other HMs. The soil Cd and Zn contents decreased vertically, but still exceeded the second level limits of Environmental Quality Standard for Soils of China (EQSS) within 80cm. The dominated soil pollutant (Cd) had higher ecological risk than Cu, Ni, Zn and Pb. The potential ecological risk (PER) factor of Cd were 65.7% and 100% in surrounding county and smelter area, respectively. The long-term smelter dust emission mainly contributed to the HMs pollution and posed serious environment risk to living beings. Copyright © 2017 Elsevier Inc. All rights reserved.

The bioleaching feasibility for Pb/Zn smelting slag and community characteristics of indigenous moderate-thermophilic bacteria.

PubMed

Cheng, Yi; Guo, Zhaohui; Liu, Xueduan; Yin, Huaqun; Qiu, Guanzhou; Pan, Fengkai; Liu, Hongwei

2009-05-01

The feasibility of recovering metal values and removing hazardous elements from the Pb/Zn smelting slag using bioleaching technique were studied through a flask experiment, and the community characteristics of the indigenous moderate-thermophilic bacteria in this bioleaching system were also analyzed through a culture-independent restriction fragment length polymorphism (RFLP) of 16S rRNA genes approach. The results show that more than 80% of Al, As, Cu, Mn, Fe and Zn in the Pb/Zn smelting slag were leached at 65(o)C, pH 1.5, pulp density 5%, but only about 5% of Pb. Phylogenetic analysis revealed that the bacteria in the bioleaching system mainly fell among Firmicutes, Gammaproteobacteria and Betaproteobacteria, and the dominant bacteria are affiliated with Bacillus spp., Sporosarcina spp. and Pseudomonas spp.

Effect of EDTA, EDDS, NTA and citric acid on electrokinetic remediation of As, Cd, Cr, Cu, Ni, Pb and Zn contaminated dredged marine sediment.

PubMed

Song, Yue; Ammami, Mohamed-Tahar; Benamar, Ahmed; Mezazigh, Salim; Wang, Huaqing

2016-06-01

In recent years, electrokinetic (EK) remediation method has been widely considered to remove metal pollutants from contaminated dredged sediments. Chelating agents are used as electrolyte solutions to increase metal mobility. This study aims to investigate heavy metal (HM) (As, Cd, Cr, Cu, Ni, Pb and Zn) mobility by assessing the effect of different chelating agents (ethylenediaminetetraacetic acid (EDTA), ethylenediaminedisuccinic acid (EDDS), nitrilotriacetic acid (NTA) or citric acid (CA)) in enhancing EK remediation efficiency. The results show that, for the same concentration (0.1 mol L(-1)), EDTA is more suitable to enhance removal of Ni (52.8 %), Pb (60.1 %) and Zn (34.9 %). EDDS provides effectiveness to increase Cu removal efficiency (52 %), while EDTA and EDDS have a similar enhancement removal effect on As EK remediation (30.5∼31.3 %). CA is more suitable to enhance Cd removal (40.2 %). Similar Cr removal efficiency was provided by EK remediation tests (35.6∼43.5 %). In the migration of metal-chelate complexes being directed towards the anode, metals are accumulated in the middle sections of the sediment matrix for the tests performed with EDTA, NTA and CA. But, low accumulation of metal contamination in the sediment was observed in the test using EDDS.

Comprehensive risk assessment and source identification of selected heavy metals (Cu, Cd, Pb, Zn, Hg, As) in tidal saltmarsh sediments of Shuangtai Estuary, China.

PubMed

Liu, Chang-Fa; Li, Bing; Wang, Yi-Ting; Liu, Yuan; Cai, Heng-Jiang; Wei, Hai-Feng; Wu, Jia-Wen; Li, Jin

2017-10-06

Heavy metals do not degrade and can remain in the environment for a long time. In this study, we analyzed the effects of Cu, Cd, Pb, Zn, Hg, and As, on environmental quality, pollutant enrichment, ecological hazard, and source identification of elements in sediments using data collected from samples taken from Shuangtai tidal wetland. The comprehensive pollution indices were used to assess environmental quality; fuzzy similarity analysis and geoaccumulation index were used to analyze pollution accumulation; correlation matrix, principal component analysis, and clustering analysis were used to analyze pollution source; environmental risk index and ecological risk index were used to assess ecological risk. The results showed that the environmental quality was either clean or almost clean. Pollutant enrichment analysis showed that the four sub-regions had similar pollution-causing metals to the background values of the soil element of the Liao River Plain, which were ranked according to their similarity. Source identification showed that all the elements were correlated. Ecological hazard analysis showed that the environmental risk index in the study area was less than zero, posing a low ecological risk. Ecological risk of the six elements was as follows: As > Cd > Hg > Cu > Pb > Zn.

Synthesis and characterization of ZnO/ZnSe NWs/PbS QDs solar cell

NASA Astrophysics Data System (ADS)

Kamruzzaman, M.; Zapien, J. A.

2017-04-01

The capture of solar energy has gained the attention for the next generation solar cell. ZnO/ZnSe NW arrays were synthesized on an FTO glass substrate using a simple and facile hydrothermal and ion-exchange approaches. The lead sulfide (PbS) QDs was infiltrated into ZnO/ZnSe NWs via SILAR method for making inorganic quantum dot sensitized ZnO/ZnSe/PbS QDs solar cell. The surface morphology, structural, optical, and J-V characteristics have been investigated. The ZnO/ZnSe NW is a core-shell like structure, and the absorption edge shifted from the UV region (ZnO NWs) to the near infrared region for ZnO/ZnSe NWs/PbS QDs. For PbS QDs-sensitized solar cell, the obtained value of η = 1.1%, J sc = 20.60 mA/cm2, V oc = 155 mV, and FF = 34.7%, respectively. The photovoltaic performance of the device in this study is still inferior. However, it is the first report regarding to ZnO/ZnZe NWs/PbS QDs solar cell. The achieving high absorption and large short circuit current density may interest in further improvement of the device performance by suppressing surface defects, optimizing the quality of ZnO/ZnSe NWs and PbS QDs.

Soil-plant abstract of heavy metals in Pb-Zn mining sites from Alcudia Valley (South Spain)

NASA Astrophysics Data System (ADS)

López-Berdonces, Miguel; Higueras, Pablo; Esbrí, Jose Maria; González-Corrochano, Beatríz; García-Noguero, Eva Mª; Martínez-Coronado, Alba; Fernandez-Calderón, Sergio; García-Noguero, Carolina

2013-04-01

Soil-plant transfer of heavy metals in Pb-Zn mining sites from Alcudia Valley (South Spain). Authors: Miguel A. López-Berdonces¹; Pablo Higueras¹; Jose María Esbrí¹; Beatriz González-Corrochano¹; Eva Mª García- Noguero¹; Alba Martínez Coronado¹; Sergio Fernández-Calderón¹; Carolina García-Noguero¹ ¹Instituto de Geología Aplicada, Universidad Castilla la Mancha, Pza. Manuel Meca, 1. 13400 Almadén, Spain. Alcudia Valley is a vast territory recently declared Natural Park, located in South of Spain. It is an area rich in mineral deposits of Zn and Pb and mining exists since the first millennium BC., having its highest ore production between mid-nineteenth century and the middle of the twentieth. This area has been selected because has more than 120 abandoned mines without remediation actions, with dumps and tailings with high contents of zinc and lead sulfides, and Cu, Ag, Cd, As, Sb in minor concentrations. In this study we determinate the transfer rate of these metals from soils to plants represented by oak leaves (Quercus ilex), because this specie is common within the selected area. To evaluate the soil-plant transfer were studied the correlation of contents, total and extractable, in soil-leaves. Extractable fraction was done by for different methods in water, EPA 1312 sulfuric acid: nitric acid 60:40 v., Ammonium Acetate and EDTA. To establish the correlation between heavy metals from soils to plants is necessary to know the contents of these and bioavailable content in soil. Three areas (S. Quintín, Romanilla, Bombita) were selected, taking 24 samples of soils and leaves. Analyzed leaves by XRF showed that Mn, Pb, Zn and Mo in S.Quintin and Romanilla, Mn, Pb in Bombita, exceeded the toxicity threshold. The same samples analyzed by ICP show us the toxicity threshold is exceeded Pb, Zn and Hg in S.Quintin, and Pb in Romanilla. The heavy metal content in leaves compared between two techniques analytical gives an acceptable correlation Zn - Pb

Behavior of Sn-0.7Cu-xZn lead free solder on physical properties and micro structure

NASA Astrophysics Data System (ADS)

Siahaan, Erwin

2017-09-01

The issues to substitute Tin-Lead Solders is concerning the health and environmental hazards that is caused by lead, and also legislative actions around the world regarding lead toxicity, which has prompted the research community to attempt to replace solder alloys for the traditional Sn-Pb alloys lead which has been used by industrial worker throughout history because it is easily extracted and refined at a relatively low energy cost and also has a range of useful properties. Traditional industry lead has been used in soldering materials for electronic applications because it has low melting point and a soft, malleable nature, when combined with tin at the eutectic composition which causes the alloy to flow easily in the liquid state and solidifies over a very small range of temperature. One of the potential candidate to replace tin-lead solder is Sn-Cu-Zn eutectic alloy as it has a lower melting temperature. Consequently, it is of interest to determine what reactions can occur in ternary systems derived from the Sn-Cu-Zn eutectic. One such system is Sn-0.7Cu-xZn. The specimen was elaborated on physical properties. The chemical content was analyzed by using Shimadzu XRD and melting point was analyzed by using Differential Scanning Calorimeter ( DSC ). The results has shown that the highest addition of Zinc content (15%Zn) will decrease the melting temperatur to 189°C compared to Sn-Pb at 183°C Increasing the amount of Zn on Sn0.7Cu-xZn alloys will decrease Cu3Sn intermetallic coumpound.

Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

NASA Astrophysics Data System (ADS)

Bigalke, Moritz; Weyer, Stefan; Kobza, Jozef; Wilcke, Wolfgang

2010-12-01

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ 65Cu, δ 66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g -1 Cu and 2084 μg g -1 Zn in the organic horizons. The δ 65Cu values varied little (-0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ 66Zn IRMM values were isotopically lighter in ash (-0.41‰) and organic horizons (-0.85‰ to -0.47‰) than in bedrock (-0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ 66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ 66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ 66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources

Zn-Cu-In-Se Quantum Dot Solar Cells with a Certified Power Conversion Efficiency of 11.6%.

PubMed

Du, Jun; Du, Zhonglin; Hu, Jin-Song; Pan, Zhenxiao; Shen, Qing; Sun, Jiankun; Long, Donghui; Dong, Hui; Sun, Litao; Zhong, Xinhua; Wan, Li-Jun

2016-03-30

The enhancement of power conversion efficiency (PCE) and the development of toxic Cd-, Pb-free quantum dots (QDs) are critical for the prosperity of QD-based solar cells. It is known that the properties (such as light harvesting range, band gap alignment, density of trap state defects, etc.) of QD light harvesters play a crucial effect on the photovoltaic performance of QD based solar cells. Herein, high quality ∼4 nm Cd-, Pb-free Zn-Cu-In-Se alloyed QDs with an absorption onset extending to ∼1000 nm were developed as effective light harvesters to construct quantum dot sensitized solar cells (QDSCs). Due to the small particle size, the developed QD sensitizer can be efficiently immobilized on TiO2 film electrode in less than 0.5 h. An average PCE of 11.66% and a certified PCE of 11.61% have been demonstrated in the QDSCs based on these Zn-Cu-In-Se QDs. The remarkably improved photovoltaic performance for Zn-Cu-In-Se QDSCs vs Cu-In-Se QDSCs (11.66% vs 9.54% in PCE) is mainly derived from the higher conduction band edge, which favors the photogenerated electron extraction and results in higher photocurrent, and the alloyed structure of Zn-Cu-In-Se QD light harvester, which benefits the suppression of charge recombination at photoanode/electrolyte interfaces and thus improves the photovoltage.

Immobilisation of Cu, Pb and Zn in Scrap Metal Yard Soil Using Selected Waste Materials.

PubMed

Kamari, A; Putra, W P; Yusoff, S N M; Ishak, C F; Hashim, N; Mohamed, A; Isa, I M; Bakar, S A

2015-12-01

Immobilisation of heavy metals in a 30-year old active scrap metal yard soil using three waste materials, namely coconut tree sawdust (CTS), sugarcane bagasse (SB) and eggshell (ES) was investigated. The contaminated soil was amended with amendments at application rates of 0 %, 1 % and 3 % (w/w). The effects of amendments on metal accumulation in water spinach (Ipomoea aquatica) and soil metal bioavailability were studied in a pot experiment. All amendments increased biomass yield and reduced metal accumulation in the plant shoots. The bioconcentration factor and translocation factor values of the metals were in the order of Zn > Cu > Pb. The addition of ES, an alternative source of calcium carbonate (CaCO3), has significantly increased soil pH and resulted in marked reduction in soil metal bioavailability. Therefore, CTS, SB and ES are promising low-cost immobilising agents to restore metal contaminated land.

Sugar beet factory lime affects the mobilization of Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn under dynamic redox conditions in a contaminated floodplain soil.

PubMed

Shaheen, Sabry M; Rinklebe, Jörg

2017-01-15

The impact of sugar beet factory lime (SBFL) on the release dynamics and mobilization of toxic metals (TMs) under dynamic redox conditions in floodplain soils has not been studied up to date. Therefore, the aim of this study was to verify the scientific hypothesis that SBFL is able to immobilize Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn under different redox potentials (E H ) in a contaminated floodplain soil. For this purpose, the non-treated contaminated soil (CS) and the same soil treated with SBFL (CS+SBFL) were flooded in the laboratory using a highly sophisticated automated biogeochemical microcosm apparatus. The experiment was conducted stepwise from reducing (-13 mV) to oxidizing (+519 mV) soil conditions. Soil pH decreased under oxic conditions in CS (from 6.9 to 4.0) and in CS+SBFL (from 7.5 to 4.4). The mobilization of Cu, Cr, Pb, and Fe were lower in CS+SBFL than in CS under both reducing/neutral and oxic/acidic conditions. Those results demonstrate that SBFL is able to decrease concentrations of these elements under a wide range of redox and pH conditions. The mobilization of Cd, Co, Mn, Mo, Ni, and Zn were higher in CS+SBFL than in CS under reducing/neutral conditions; however, these concentrations showed an opposite behavior under oxic/acidic conditions and were lower in CS+SBFL than in CS. We conclude that SBFL immobilized Cu, Cr, Pb, and Fe under dynamic redox conditions and immobilized Cd, Co, Mn, Mo, Ni, and Zn under oxic acidic conditions; however, the latter elements were mobilized under reducing neutral conditions in the studied soil. Therefore, the addition of SBFL to acid floodplain soils contaminated with TMs might be an important alternative for ameliorating these soils with view to a sustainable management of these soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Detection of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases in co-evaporated Cu2ZnSnSe4 thin-films

NASA Astrophysics Data System (ADS)

Schwarz, Torsten; Marques, Miguel A. L.; Botti, Silvana; Mousel, Marina; Redinger, Alex; Siebentritt, Susanne; Cojocaru-Mirédin, Oana; Raabe, Dierk; Choi, Pyuck-Pa

2015-10-01

Cu2ZnSnSe4 thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu2ZnSnSe4 and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases. Possible effects of these phases on solar cell performance are discussed.

A comparison of the properties of polyurethane immobilised Sphagnum moss, seaweed, sunflower waste and maize for the biosorption of Cu, Pb, Zn and Ni in continuous flow packed columns.

PubMed

Zhang, Yue; Banks, Charles

2006-02-01

The biosorption of Cu, Pb, Zn and Ni from a mixed solution of the metals was investigated in continuous flow packed columns containing polyurethane immobilised biomass. The characteristics and biosorption properties of Sphagnum moss, the brown seaweed Ascophyllum nodosum, waste biomass from the preparation of sunflower oil, and whole plant maize were compared. All the biomass types showed a preference for the sequestration of Pb followed by Cu, with Ni and Zn having roughly equal affinity. With continuous metal loading to the column there was an initial binding of all metals and then a displacement of the lower affinity metals by those with a high affinity. This led to a chromatographic effect in the column with breakthrough concentrations for low-affinity metals higher than the concentration in the feed. A similar phenomenon was found on desorption using acidic solutions where low-affinity metals were desorbed preferentially. The results also indicated that despite competitive displacement of one metal species by another the biomass appeared to succeed in retaining some low-affinity metal species indicating that there may be selective sites present with different affinity characteristics. When using a multi-metal solution with Cu, Pb, Zn and Ni at equal 10 mgl(-1) concentrations as column influent, the total quantities of metal sequestered were: seaweed, 117.3 mg g(-1); sunflower waste, 33.2 mg g(-1); Sphagnum moss, 32.5 mg g(-1); and maize, 2.3 mg g(-1). The use of an acid base potentiometric titration showed a relationship between the number of acid functional groups and biosorption capacity, although this was not proportional for the biomass types studied. It can, however, be used in conjunction with a simple classification of metals into high and low-affinity bands to make a preliminary assessment of a biosorption system.

Effects of Cd, Pb, Zn, Cu-resistant endophytic Enterobacter sr CBSB1 and Rhodotorula sp. CBSB79 on the growth and phytoextraction of Brassica plants in multimetal contaminated soils.

PubMed

Wang, Wenfeng; Deng, Zujun; Tan, Hongming; Cao, Lixiang

2013-01-01

To survey the effects of endophytic Enterobacter sp. CBSB1 and Rhodotorula sp. CBSB79 resistant to Cd2+, Pb2+, Zn2+, and Cu2+ on the growth and phytoextraction of Brassica, the endophytes were isolated by surface- sterilized methods and characterized. The CBSB1 significantly increased 44.2% of the dry weight of Brassica napus in the multimetal contaminated soil (P < 0.05) and showed no effect or declined the dry weight of B. alboglabra, B. campestris ssp. chinensis var. cummunis, B. campestris ssp. chinensis var. utilis cv. Youqing12, B. campestris ssp. chinensis var. utilis cv. Lvbao701 plants. The dry weights of B. napus, B. campestris ssp. chinensis var. utilis, and B. alboglabra showed a significant increase when the CBSB79 was inoculated (P < 0.05). In general, inoculation with bacteria and yeast did not greatly alter the metal concentration in plant tissues. Compared to Enterobacter sp. CBSB1, the yeast Rhodotorula sp CBSB79 showed higher potentials to improve extraction efficacy of Cd, Pb, Zn, and Cu by Brassica seedlings in the field.

Geographical and pedological drivers of distribution and risks to soil fauna of seven metals (Cd, Cu, Cr, Ni, Pb, V and Zn) in British soils.

PubMed

Spurgeon, David J; Rowland, Philip; Ainsworth, Gillian; Rothery, Peter; Long, Sara; Black, Helaina I J

2008-05-01

Concentrations of seven metals were measured in over 1000 samples as part of an integrated survey. Sixteen metal pairs were significantly positively correlated. Cluster analysis identified two clusters. Metals from the largest (Cr, Cu, Ni, V, Zn), but not the smallest (Cd, Pb) cluster were significantly negatively correlated with spatial location and soil pH and organic matter content. Cd and Pb were not correlated with these parameters, due possibly to the masking effect of recent extensive release. Analysis of trends with soil properties in different habitats indicated that general trends may not necessarily be applicable to all areas. A risk assessment indicated that Zn poses the most widespread direct risk to soil fauna and Cd the least. Any risks associated with high metal concentrations are, however, likely to be greatest in habitats such as arable and horticultural, improved grassland and built up areas where soil metal concentrations are more frequently elevated.

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn.

PubMed

Scancar, J; Milacic, R; Strazar, M; Burica, O; Bukovec, P

2001-02-01

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.

An ICP-MS procedure to determine Cd, Co, Cu, Ni, Pb and Zn in oceanic waters using in-line flow-injection with solid-phase extraction for preconcentration.

PubMed

O'Sullivan, Jeanette E; Watson, Roslyn J; Butler, Edward C V

2013-10-15

An automated procedure including both in-line preconcentration and multi-element determination by an inductively coupled plasma mass spectrometer (ICP-MS) has been developed for the determination of Cd, Co, Cu, Ni, Pb and Zn in open-ocean samples. The method relies on flow injection of the sample through a minicolumn of chelating (iminodiacetate) sorbent to preconcentrate the trace metals, while simultaneously eliminating the major cations and anions of seawater. The effectiveness of this step is tested and reliability in results are secured with a rigorous process of quality assurance comprising 36 calibration and reference samples in a run for analysis of 24 oceanic seawaters in a 6-h program. The in-line configuration and procedures presented minimise analyst operations and exposure to contamination. Seawater samples are used for calibration providing a true matrix match. The continuous automated pH measurement registers that chelation occurs within a selected narrow pH range and monitors the consistency of the entire analytical sequence. The eluent (0.8M HNO3) is sufficiently strong to elute the six metals in 39 s at a flow rate of 2.0 mL/min, while being compatible for prolonged use with the mass spectrometer. Throughput is one sample of 7 mL every 6 min. Detection limits were Co 3.2 pM, Ni 23 pM, Cu 46 pM, Zn 71 pM, Cd 2.7 pM and Pb 1.5 pM with coefficients of variation ranging from 3.4% to 8.6% (n=14) and linearity of calibration established beyond the observed concentration range of each trace metal in ocean waters. Recoveries were Co 96.7%, Ni 102%, Cu 102%, Zn 98.1%, Cd 92.2% and Pb 97.6%. The method has been used to analyse ~800 samples from three voyages in the Southern Ocean and Tasman Sea. It has the potential to be extended to other trace elements in ocean waters. © 2013 Elsevier B.V. All rights reserved.

Reduced Carrier Recombination in PbS - CuInS2 Quantum Dot Solar Cells

PubMed Central

Sun, Zhenhua; Sitbon, Gary; Pons, Thomas; Bakulin, Artem A.; Chen, Zhuoying

2015-01-01

Energy loss due to carrier recombination is among the major factors limiting the performance of TiO2/PbS colloidal quantum dot (QD) heterojunction solar cells. In this work, enhanced photocurrent is achieved by incorporating another type of hole-transporting QDs, Zn-doped CuInS2 (Zn-CIS) QDs into the PbS QD matrix. Binary QD solar cells exhibit a reduced charge recombination associated with the spatial charge separation between these two types of QDs. A ~30% increase in short-circuit current density and a ~20% increase in power conversion efficiency are observed in binary QD solar cells compared to cells built from PbS QDs only. In agreement with the charge transfer process identified through ultrafast pump/probe spectroscopy between these two QD components, transient photovoltage characteristics of single-component and binary QDs solar cells reveal longer carrier recombination time constants associated with the incorporation of Zn-CIS QDs. This work presents a straightforward, solution-processed method based on the incorporation of another QDs in the PbS QD matrix to control the carrier dynamics in colloidal QD materials and enhance solar cell performance. PMID:26024021

Abundant defects and defect clusters in kesterite Cu2ZnSnS4 and Cu2ZnSnSe4

NASA Astrophysics Data System (ADS)

Chen, Shiyou; Wang, Lin-Wang; Walsh, Aron; Gong, Xin-Gao; Wei, Su-Huai

2013-03-01

Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing intensive attention as the light-absorber materials in thin-film solar cells. A large variety of intrinsic defects can be formed in these quaternary semiconductors, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. We will present our first-principles calculation study on a series of intrinsic defects and defect clusters in Cu2ZnSnS4 and Cu2ZnSnSe4, and discuss: (i) strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the dominant CuZn antisites and Cu vacancies which determine the intrinsic p-type conductivity, and their dependence on the elemental ratios; (iii) the high population of charge-compensated defect clusters (like VCu + ZnCu and 2CuZn + SnZn) and their contribution to non-stoichiometry ; (iv) the deep-level defects which act as recombination centers. Based on the calculation, we will explain the experimental observation that Cu poor and Zn rich conditions give the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells with high S composition. Supported by NSF of China, JCAP: a U.S. DOE Energy Innovation Hub, Royal Society of U.K. and EPSRC, and U.S. DOE.

Measurements of labile Cd, Cu, Ni, Pb, and Zn levels at a northeastern Brazilian coastal area under the influence of oil production with diffusive gradients in thin films technique (DGT).

PubMed

de Souza, João M; Menegário, Amauri A; de Araújo Júnior, Marcus A G; Francioni, Eleine

2014-12-01

In this work, the ability of the diffusive gradients in thin films technique (DGT) was evaluated for monitoring the concentrations, and estimating the availability, of metals at a northeastern Brazilian coastal area under the influence of oil production. Three sites with an average distance between 0m (EM-1), 100 m (EM-2), and 1,000 m (EM-3) of a submarine outfall-I (Guamaré-RN, Brazil) and another site (GA-1) with an average distance of 12,000 m east of Outfall I, near the city of Galinhos, were studied. DGT units were deployed at the same sites in three campaigns from July, 2010 to June, 2011. Effects on the accuracy of analytical results regarding the deployment time, gel porosity, and thickness were evaluated. There was no difference between the measurements obtained with two sets of DGT devices, those assembled with open or restrictive pore gel, respectively, showing that organic metallic species are not present near the submarine outlet. After 21 day deployments in a region (near Submarine Outfall I) that receives produced waters that have been treated, there was evidence of biofilm formation on DGT membranes. However, it was demonstrated that the biofilm interference with DGT measurements was negligible. Data found in this work show that total concentrations of Cd, Cu, Pb, Ni, and Zn in seawater samples collected at sites GA-1 and EM-1 in two campaigns were below 0.33, 1.67, 0.47, 0.70, 2.86 ng mL(-1) respectively. For the first time, labile levels of Cd, Cu, Pb, Ni, and Zn in an area under the influence of oil production were determined. DGT measurements allowed the verification of the effects of temporal variation on levels of Zn and Ni. There were no effects of spatial variations on levels of Cd, Cu, Ni, Pb, and Zn at the four studied sites, suggesting no contamination of these metals at the northeastern Brazilian coastal area investigated in this work. Copyright © 2014. Published by Elsevier B.V.

Origin and tectonic implications of the Zhaxikang Pb-Zn-Sb-Ag deposit in northern Himalaya: evidence from structures, Re-Os-Pb-S isotopes, and fluid inclusions

NASA Astrophysics Data System (ADS)

Zhou, Qing; Li, Wenchang; Qing, Chengshi; Lai, Yang; Li, Yingxu; Liao, Zhenwen; Wu, Jianyang; Wang, Shengwei; Dong, Lei; Tian, Enyuan

2018-04-01

The Zhaxikang Pb-Zn-Sb-Ag-(Au) deposits, located in the eastern part of northern Himalaya, totally contain more than 1.146 million tonnes (Mt) of Pb, 1.407 Mt of Zn, 0.345 Mt of Sb, and 3 kilotonnes (kt) of Ag. Our field observations suggest that these deposits are controlled by N-S trending and west- and steep-dipping normal faults, suggesting a hydrothermal rather than a syngenetic sedimentary origin. The Pb-Zn-Sb-Ag-(Cu-Au) mineralization formed in the Eocene as indicated by a Re-Os isochron age of 43.1 ± 2.5 Ma. Sulfide minerals have varying initial Pb isotopic compositions, with (206Pb/204Pb)i of 19.04-19.68, (207Pb/204Pb)i of 15.75-15.88, and (208Pb/204Pb)i of 39.66-40.31. Sulfur isotopic values display a narrow δ34S interval of +7.8-+12.2‰. These Pb-S isotopic data suggest that the Zhaxikang sources of Pb and S should be mainly from the coeval felsic magmas and partly from the surrounding Mesozoic strata including metasedimentary rocks and layered felsic volcanic rocks. Fluid inclusion studies indicate that the hydrothermal fluids have medium temperatures (200-336 °C) but varying salinities (1.40-18.25 wt.% NaCl equiv.) with densities of 0.75-0.95 g/cm3, possibly suggesting an evolution mixing between a high salinity fluid, perhaps of magmatic origin, with meteoric water.

H2 gas sensing properties of a ZnO/CuO and ZnO/CuO/Cu2O Heterostructures

NASA Astrophysics Data System (ADS)

Ababii, N.; Postica, V.; Hoppe, M.; Adelung, R.; Lupan, O.; Railean, S.; Pauporté, T.; Viana, B.

2017-03-01

The most important parameters of gas sensors are sensitivity and especially high selectivity to specific chemical species. To improve these parameters we developed sensor structures based on layered semiconducting oxides, namely CuO/Cu2O, CuO:Zn/Cu2O:Zn, NiO/ZnO. In this work, the ZnO/CuxO (where x = 1, 2) bi-layer heterostructure were grown via a simple synthesis from chemical solution (SCS) at relatively low temperatures (< 95 °C), representing a combination of layered n-type and p-type semiconducting oxides which are widely used as sensing material for gas sensors. The main advantages of the developed device structures are given by simplicity of the synthesis and technological cost-efficiency. Structural investigations showed high crystallinity of synthesized layers confirming the presence of zinc oxide nanostructures on the surface of the copper oxide film deposited on glass substrate. Structural changes in morphology of grown nanostructures induced by post-grown thermal annealing were observed by scanning electron microscopy (SEM) investigations, and were studied in detail. The influence of thermal annealing type on the optical properties was also investigated. As an example of practical applications, the ZnO/CuxO bi-layer heterojunctions and ZnO/CuO/Cu2O three-layered structures were integrated into sensor structures and were tested to different types of reducing gases at different operating temperatures (OPT), showing promising results for fabrication of selective gas sensors.

Cyclotron production of 61Cu using natural Zn & enriched 64Zn targets

NASA Astrophysics Data System (ADS)

Asad, A. H.; Smith, S. V.; Chan, S.; Jeffery, C. M.; Morandeau, L.; Price, R. I.

2012-12-01

Copper-61 (61Cu) shares with 64Cu certain advantages for PET diagnostic imaging, but has a shorter half-life (3.4hr vs. 12.7hr) and a greater probability of positron production per disintegration (61% vs. 17.9%). One important application is for in vivo imaging of hypoxic tissue. In this study 61Cu was produced using the 64Zn(p,α)61Cu reaction on natural Zn or enriched 64Zn targets. The enriched 64Zn (99.82%) was electroplated onto high purity gold or silver foils or onto thin Al discs. A typical target bombardment used 30μA; at 11.7, 14.5 or 17.6MeV over 30-60min. The 61Cu (radiochemical purity of >95%) was separated using a combination of cation and anion exchange columns. The 64Zn target material was recovered after each run, for re-use. In a direct comparison with enriched 64Zn-target results, 61Cu production using the cheaper natZn target proved to be an effective alternative.

Heavy metals and health risk assessment of arable soils and food crops around Pb-Zn mining localities in Enyigba, southeastern Nigeria

NASA Astrophysics Data System (ADS)

Obiora, Smart C.; Chukwu, Anthony; Davies, Theophilus C.

2016-04-01

This study determined the heavy metals concentration in arable soils and associated food crops around the Pb-Zn mines in Enyigba, Nigeria, and metal transfer factors were calculated. Air-dried samples of the soils and food crops were analyzed for 8 known nutritional and toxic heavy metals by Inductively Coupled Plasma - Mass Spectrometer (ICP-MS) method. Eighty seven percent of all the 20 sampled soils contain Pb in excess of the maximum allowable concentration (MAC) set by Canadian Environmental Quality Guideline (CCME) and European Union (EU) Standard, while Zn in thirty-one percent of the samples exceeded the CCME for MAC of 200 mg/kg. All the food crops, with the exception of yam tuber, contain Pb which exceeded the 0.43 mg/kg and 0.3 mg/kg MAC standards of EU and WHO/FAO respectively, with the leafy vegetables accumulating more Pb than the tubers. The metal transfer factors in the tubers and the leafy vegetables were in the order: Mo > Cu > Zn > Mn > As > Cd > Cr > Ni > Pb and Cd > Cu > Zn > Mn > Mo > As > Ni > Pb > Cr, respectively. Risk assessment studies revealed no health risk in surrounding populations for most of the heavy metals. However, Pb had a high health risk index (HRI) of 1.1 and 1.3, in adults and children, respectively for cassava tuber; Pb had HRI > 1 in lemon grass while Mn also had HRI > 1 in all the leafy vegetables for both adult and children. This high level of HRI for Pb and Mn is an indication that consumers of the food crops contaminated by these metals are at risk of health problems such as Alzheimers' disease and Manganism, associated with excessive intake of these metals. Further systematic monitoring of heavy metal fluxes in cultivable soils around the area of these mines is recommended.

Monitoring of Cr, Cu, Pb, V and Zn in polluted soils by laser induced breakdown spectroscopy (LIBS).

PubMed

Dell'Aglio, Marcella; Gaudiuso, Rosalba; Senesi, Giorgio S; De Giacomo, Alessandro; Zaccone, Claudio; Miano, Teodoro M; De Pascale, Olga

2011-05-01

Laser Induced Breakdown Spectroscopy (LIBS) is a fast and multi-elemental analytical technique particularly suitable for the qualitative and quantitative analysis of heavy metals in solid samples, including environmental ones. Although LIBS is often recognised in the literature as a well-established analytical technique, results about quantitative analysis of elements in chemically complex matrices such as soils are quite contrasting. In this work, soil samples of various origins have been analyzed by LIBS and data compared to those obtained by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The emission intensities of one selected line for each of the five analytes (i.e., Cr, Cu, Pb, V, and Zn) were normalized to the background signal, and plotted as a function of the concentration values previously determined by ICP-OES. Data showed a good linearity for all calibration lines drawn, and the correlation between ICP-OES and LIBS was confirmed by the satisfactory agreement obtained between the corresponding values. Consequently, LIBS method can be used at least for metal monitoring in soils. In this respect, a simple method for the estimation of the soil pollution degree by heavy metals, based on the determination of an anthropogenic index, was proposed and determined for Cr and Zn.

Potential use of lime combined with additives on (im)mobilization and phytoavailability of heavy metals from Pb/Zn smelter contaminated soils.

PubMed

Hussain Lahori, Altaf; Zhang, Zengqiang; Guo, Zhanyu; Mahar, Amanullah; Li, Ronghua; Kumar Awasthi, Mukesh; Ali Sial, Tanveer; Kumbhar, Farhana; Wang, Ping; Shen, Feng; Zhao, Junchao; Huang, Hui

2017-11-01

This explorative study was aimed to assess the efficiency of lime alone and in combined with additives to immobilize Pb, Cd, Cu and Zn in soil and reduce their phytoavailability for plant. A greenhouse pot experiment was performed by using low and heavily contaminated top soils viz. Tongguan contaminated (TG-C); Fengxian heavily contaminated (FX-HC) and Fengxian low contaminated (FX-LC). The contaminated soils were treated with lime (L) alone and in combined with Ca-bentonite (CB), Tobacco biochar (TB) and Zeolite (Z) at 1% and cultivated by Chinese cabbage (Brassica campestris L). Results revealed that all amendments (p< 0.05) significantly reduced the DTPA-extractable Pb 97.33, Cd 68.06 and Cu 91.11% with L+TB, L+CB, L+Z in FX-LC soil and Zn 87.12% respectively, with L+CB into TG-C soil. Consequently, the application of lime alone and in combined with additives were drastically decreased the dry biomass yield of Brassica campestris L. as compared with control. Thus, these feasible amendments potentially maximum reduced the uptake by plant shoots upto Pb 53.47 and Zn 67.93% with L+Z and L+TB in FX-LC soil, while Cd 68.58 and Cu 60.29% with L+TB, L+CB in TG-C soil but Cu uptake in plant shoot was observed 27.26% and 30.17% amended with L+TB and L+Z in FX-HC and FX-LC soils. On the other hand, these amendments were effectively reduced the potentially toxic metals (PTMs) in roots upto Pb77.77% L alone in FX-HC, Cd 96.76% with L+TB in TG-C, while, Cu 66.70 and Zn 60.18% with L+Z in FX-LC. Meanwhile, all amendments were responsible for increasing soil pH and CEC but decreased soils EC level. Based on this result, these feasible soil amendments were recommended for long term-study under field condition to see the response of another hyper accumulator crop. Copyright © 2017. Published by Elsevier Inc.

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

USGS Publications Warehouse

Balistrieri, L.S.; Blank, R.G.

2008-01-01

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

Simultaneous adsorption and degradation of Zn(2+) and Cu (2+) from wastewaters using nanoscale zero-valent iron impregnated with clays.

PubMed

Shi, Li-Na; Zhou, Yan; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

2013-06-01

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu(2+) and Zn(2+) from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu(2+) and Zn(2+) from a aqueous solution containing a 100 mg/l of Cu(2+) and Zn(2+), where 92.9 % Cu(2+) and 58.3 % Zn(2+) were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu(2+) and Zn(2+). A kinetics study indicated that removing Cu(2+) and Zn(2+) with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu(2+)and Zn(2+) on bentonite and the degradation of Cu(2+)and Zn(2+) by nZVI on the bentonite. However, Cu(2+) removal by B-nZVI was reduced rather than adsorption, while Zn(2+) removal was main adsorption. Finally, Cu(2+), Zn(2+), Ni(2+), Pb(2+) and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.

Aided phytoextraction of Cu, Pb, Zn, and As in copper-contaminated soils with tobacco and sunflower in crop rotation: Mobility and phytoavailability assessment.

PubMed

Hattab-Hambli, Nour; Motelica-Heino, Mikael; Mench, Michel

2016-02-01

Copper-contaminated soils were managed with aided phytoextraction in 31 field plots at a former wood preservation site, using a single incorporation of compost (OM) and dolomitic limestone (DL) followed by a crop rotation with tobacco and sunflower. Six amended plots, with increasing total soil Cu, and one unamended plot were selected together with a control uncontaminated plot. The mobility and phytoavailability of Cu, Zn, Cr and As were investigated after 2 and 3 years in soil samples collected in these eight plots. Total Cu, Zn, Cr and As concentrations were determined in the soil pore water (SPW) and available soil Cu and Zn fractions by DGT. The Cu, Zn, Cr and As phytoavailability was characterized by growing dwarf beans on potted soils and determining the biomass of their plant parts and their foliar ionome. Total Cu concentrations in the SPW increased with total soil Cu. Total Cu, Zn, Cr and As concentrations in the SPW decreased in year 3 as compared to year 2, likely due to annual shoot removals by the plants and the lixiviation. Available soil Cu and Zn fractions also declined in year 3. The Cu, Zn, Cr and As phytoavailability, assessed by their concentration and mineral mass in the primary leaves of beans, was reduced in year 3. Copyright © 2015 Elsevier Ltd. All rights reserved.

Size-depressed critical temperatures for the order-disorder transition of FePt, CoPt, FePb, Cu2S, and ZnS nanostructures

NASA Astrophysics Data System (ADS)

Jiang, R.; Zhou, Z. F.; Yang, X. X.; Guo, N. G.; Qi, W. H.; Sun, C. Q.

2013-01-01

The size dependency of the critical temperature (TC) for the order-disorder phase transitions of both the bimetallic and the chalcogenide nanoclusters is shown to follow the rule of bond order-length-strength correlation. The loss of the cohesive energy of the undercoordinated atoms in the surface skin dictates the structural stability. Theoretical reproduction of the size TC trends of FePt, CoPt, FePb, Cu2S, and ZnS nanostructures not only confirms our expectations without involving the concepts of surface energy or entropy used for continuum bulk materials but also provides guideline for engineering nanostructured alloys or compounds.

A field method using microcosms to evaluate transfer of Cd, Cu, Ni, Pb and Zn from sewage sludge amended forest soils to Helix aspersa snails.

PubMed

Scheifler, R; Ben Brahim, M; Gomot-de Vaufleury, A; Carnus, J-M; Badot, P-M

2003-01-01

Juvenile Helix aspersa snails exposed in field microcosms were used to assess the transfer of Cd, Cu, Ni, Pb and Zn from forest soils amended with liquid and composted sewage sludge. Zn concentrations and contents were significantly higher in snails exposed to liquid and composted sludge after 5 and 7 weeks of exposure, when compared with control. Trends were less clear for the other metals. Present results show that Zn, among the cocktail of metallic trace elements (MTE) coming from sewage sludge disposal, represents the principal concern for food chain transfer and secondary poisoning risks. The microcosm design used in this experiment was well suited for relatively long-term (about 2 months) active biomonitoring with H. aspersa snails. The snails quickly indicated the variations of MTE concentrations in their immediate environment. Therefore, the present study provides a simple but efficient field tool to evaluate MTE bioavailability and transfer.

Chemical Synthesis of ZnS:Cu Nanosheets

NASA Astrophysics Data System (ADS)

Bodo, Bhaskarjyoti; Kalita, P. K.

2010-10-01

ZnS thin films are synthesized through chemical bath deposition (CBD) technique from aqueous solution of ZnSO4 and thiourea mixing in equal volume and equimolar ratio. A 1% CuSO4 solution is mixed with the ZnSO4 solution for doping before the final chemical reaction. SEM image shows the formation of mainly nanosheets, teeth and comb like structures. Absorption studies show red shift of enhanced band gap on Cu doping. Photoluminescence of ZnS:Cu reveals the enhancement of blue luminescence at 468 nm and low intensity green emission at 493 nm which is attributed to more Cu2+ lying in the interstices. XRD shows that the prepared ZnS nanophosphors possess cubic zinc blende structures.

Historical perspective of heavy metals contamination (Cd, Cr, Cu, Hg, Pb, Zn) in the Seine River basin (France) following a DPSIR approach (1950-2005).

PubMed

Meybeck, Michel; Lestel, Laurence; Bonté, Philippe; Moilleron, Régis; Colin, Jean Louis; Rousselot, Olivier; Hervé, Daniel; de Pontevès, Claire; Grosbois, Cécile; Thévenot, Daniel R

2007-04-01

The Driver-Pressures-State-Impact-Response approach is applied to heavy metals in the Seine River catchment (65,000 km(2); 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930-2000 for floodplain cores, 1980-2003 for suspended particulate matter (SPM) and bed-sediments, 1994-2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg(-1) for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1.8 mg kg(-1)), Hg (1.08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970's and the metal monitoring in the catchment that started in the early 1980's. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990's, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very

Complete transformation of ZnO and CuO nanoparticles in ...

EPA Pesticide Factsheets

Here, we present evidence on complete transformation of ZnO and CuO nanoparticles, which are among the most heavily studied metal oxide particles, during 24 h in vitro toxicological testing with human T-lymphocytes. Synchrotron radiation-based X-ray absorption near edge structure (XANES) spectroscopy results revealed that Zn speciation profiles of 30 nm and 80 nm ZnO nanoparticles, and ZnSO4- exposed cells were almost identical with the prevailing species being Zn-cysteine. This suggests that ZnO nanoparticles are rapidly transformed during a standard in vitro toxicological assay, and are sequestered intracellularly, analogously to soluble Zn. Complete transformation of ZnO in the test conditions was further supported by almost identical Zn spectra in medium to which ZnO nanoparticles or ZnSO4 was added. Likewise, Cu XANES spectra for CuO and CuSO4-exposed cells and cell culture media were similar. These results together with our observation on similar toxicological profiles of ZnO and soluble Zn, and CuO and soluble Cu, underline the importance of dissolution and subsequent transformation of ZnO and CuO nanoparticles during toxicological testing and provide evidence that the nano-specific effect of ZnO and CuO nanoparticulates is negligible in this system. We strongly suggest to account for this aspect when interpreting the toxicological results of ZnO and CuO nanoparticles. Although a number of studies have discussed the transformation of nanoparticles during

Interfacial Phenomena in Al/Al, Al/Cu, and Cu/Cu Joints Soldered Using an Al-Zn Alloy with Ag or Cu Additions

NASA Astrophysics Data System (ADS)

Pstruś, Janusz; Gancarz, Tomasz

2014-05-01

The studies of soldered joints were carried out in systems: Al/solder/Al, Al/solder/Cu, Cu/solder/Cu, where the solder was (Al-Zn)EUT, (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Ag and (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Cu addition. Brazing was performed at 500 °C for 3 min. The EDS analysis indicated that the composition of the layers starting from the Cu pad was CuZn, Cu5Zn8, and CuZn4, respectively. Wetting tests were performed at 500 °C for 3, 8, 15, and 30 min, respectively. Thickness of the layers and their kinetics of growth were measured based on the SEM micrographs. The formation of interlayers was not observed from the side of Al pads. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed.

Mineralogical, textural, sulfur and lead isotope constraints on the origin of Ag-Pb-Zn mineralization at Bianjiadayuan, Inner Mongolia, NE China

NASA Astrophysics Data System (ADS)

Zhai, Degao; Liu, Jiajun; Cook, Nigel J.; Wang, Xilong; Yang, Yongqiang; Zhang, Anli; Jiao, Yingchun

2018-04-01

The Bianjiadayuan Ag-Pb-Zn deposit (4.81 Mt. @157.4 g/t Ag and 3.94% Pb + Zn) is located in the Great Hinggan Range Pb-Zn-Ag-Cu-Mo-Sn-Fe polymetallic metallogenic belt, NE China. Vein type Pb-Zn-Ag ore bodies are primarily hosted by slate, adjacent to a Sn ± Cu ± Mo mineralized porphyry intrusion. The deposit is characterized by silver-rich ores with Ag grades up to 3000 g/t. Four primary paragenetic sequences are recognized: (I) arsenopyrite + pyrite + quartz, (II) main sulfide + quartz, (III) silver-bearing sulfosalt + quartz, and (IV) boulangerite + calcite. A subsequent supergene oxidation stage has also been identified. Hydrothermal alteration consists of an early episode of silicification, two intermediate episodes (propylitic and phyllic), and a late argillic episode. Silver mineralization primarily belongs to the late paragenetic sequence III. Freibergite is the dominant and most important Ag-mineral in the deposit. Detailed ore mineralogy of Bianjiadayuan freibergite reveals evidence of chemical heterogeneity down to the microscale. Silver-rich sulfosalts in the late paragenetic sequence III are largely derived from a series of retrograde and solid-state reactions that redistribute Ag via decomposition and exsolution during cooling, illustrating that documentation of post-mineralization processes is essential for understanding silver ore formation. Sulfur and lead isotope compositions of sulfides, and comparison with those of local various geological units, indicate that the ore-forming fluids, lead, and other metals have a magmatic origin, suggesting a close genetic association between the studied Ag-Pb-Zn veins and the local granitic intrusion. Fluid cooling coupled with decreases in fO2 and fS2 are the factors inferred to have led to a decrease of silver solubility in the hydrothermal fluid, and successively promoted extensive Ag deposition.

Primary fragmentation pathways of gas phase [M(uracil-H)(uracil)]+ complexes (M=Zn, Cu, Ni, Co, Fe, Mn, Cd, Pd , Mg, Ca, Sr, Ba, and Pb): loss of uracil versus HNCO.

PubMed

Ali, Osama Y; Randell, Nicholas M; Fridgen, Travis D

2012-04-23

Complexes formed between metal dications, the conjugate base of uracil, and uracil are investigated by sustained off-resonance irradiation collision-induced dissociation (SORI-CID) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Positive-ion electrospray spectra show that [M(Ura-H)(Ura)](+) (M=Zn, Cu, Ni, Co, Fe, Mn, Cd, Pd, Mg, Ca, Sr, Ba, or Pb) is the most abundant ion even at low concentrations of uracil. SORI-CID experiments show that the main primary decomposition pathway for all [M(Ura-H)(Ura)](+) , except where M=Ca, Sr, Ba, or Pb, is the loss of HNCO. Under the same SORI-CID conditions, when M is Ca, Sr, Ba, or Pb, [M(Ura-H)(Ura)](+) are shown to lose a molecule of uracil. Similar results were observed under infrared multiple-photon dissociation excitation conditions, except that [Ca(Ura-H)(Ura)](+) was found to lose HNCO as the primary fragmentation product. The binding energies between neutral uracil and [M(Ura-H)](+) (M=Zn, Cu, Ni, Fe, Cd, Pd ,Mg, Ca, Sr Ba, or Pb) are calculated by means of electronic-structure calculations. The differences in the uracil binding energies between complexes which lose uracil and those which lose HNCO are consistent with the experimentally observed differences in fragmentation pathways. A size dependence in the binding energies suggests that the interaction between uracil and [M(Ura-H)](+) is ion-dipole complexation and the experimental evidence presented supports this. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glassy behavior of diluted Cu-Zn ferrites

NASA Astrophysics Data System (ADS)

Akhter, Shahida; Hakim, M. A.; Hoque, S. M.; Mathieu, R.; Nordblad, P.

2018-04-01

The magnetic behavior of Zn substituted Cu-Zn spinel ferrites having chemical formula Cu1-xZnxFe2O4 (x = 0.7, 0.8, 0.9 and 1.0) has been studied by SQUID magnetometry, by means of magnetic hysteresis, field-cooled (FC) and zero-field-cooled (ZFC) magnetization, memory effect and low field ac susceptibility measurements. These measurements suggest that the ferrimagnetic phase of the x ≤ 0.8 samples is gradually turned into a spin glass (x ≥ 0.9). The compound with x = 0.9 exhibits the typical dynamical behavior of spin glasses, with indication of aging, rejuvenation and memory effects. The evolution of the magnetic properties of Cu-Zn spinel ferrites with substitution of Zn for Cu is discussed.

Characterization of cadmium biosorption by Exiguobacterium sp. isolated from farmland soil near Cu-Pb-Zn mine.

PubMed

Park, Jin Hee; Chon, Hyo-Taek

2016-06-01

Bacteria have the ability to bind heavy metals on their cell wall. Biosorption is a passive and energy-independent mechanism to adsorb heavy metals. The efficiency of heavy metal biosorption can vary depending on several factors such as the growth phase of bacteria, solution pH, and existence of competitive heavy metals. In this study, Exiguobacterium sp. isolated from farmland soil near a mine site were used, and optimal conditions for Cd biosorption in solution were investigated. As bacterial growth progressed, Cd biosorption increased, which is attributed to changes in the structure and composition of the cell wall during bacterial growth. The biosorption process was rapid and was completed within 30 min. Cadmium biosorption was highest at pH 7 due to the dissociation of hydrogen ions and the increase of negative charges with increasing pH. In the mixed metal solution of Cd, Pb, and Zn, the amount of biosorption was in the order of Pb>Cd>Zn while in a single metal solution, the order was Cd≥Pb>Zn. The maximum adsorption capacity for Cd by the isolated bacteria was 15.6 mg/g biomass, which was calculated from the Langmuir isotherm model. Different adsorption efficiencies under various environmental conditions indicate that, to control metal mobility, the conditions for biosorption should be optimized before applying bacteria. The results showed that the isolated bacteria can be used to immobilize metals in metal-contaminated wastewater.

Genotoxicity and cytotoxicity response to environmentally relevant complex metal mixture (Zn, Cu, Ni, Cr, Pb, Cd) accumulated in Atlantic salmon (Salmo salar). Part I: importance of exposure time and tissue dependence.

PubMed

Stankevičiūtė, Milda; Sauliutė, Gintarė; Svecevičius, Gintaras; Kazlauskienė, Nijolė; Baršienė, Janina

2017-10-01

Health impact of metal mixture at environment realistic concentrations are difficult to predict especially for long-term effects where cause-and-effect relationships may not be directly obvious. This study was aimed to evaluate metal mixture (Zn-0.1, Cu-0.01, Ni-0.01, Cr-0.01, Pb-0.005 and Cd-0.005 mg/L, respectively for 1, 2, 4, 7, 14 and 28 days at concentrations accepted for the inland waters in EU) genotoxicity (micronuclei, nuclear buds, nuclear buds on filament), cytotoxicity (8-shaped nuclei, fragmented-apoptotic erythrocytes), bioaccumulation, steady-state and the reference level of geno-cytotoxicity in hatchery-reared Atlantic salmon tissues. Metals accumulated mostly in gills and kidneys, to the lesser extent in the muscle. Uptake of metals from an entire mixture in the fish for 14 days is sufficient to reach steady-state Cr, Pb concentrations in all tissues; Zn, Cu-in kidneys and muscle, Ni-in liver, kidneys, muscle and Cd-in muscle. Treatment with metal mixture significantly increased summed genotoxicity levels at 7 days of exposure in peripheral blood and liver erythrocytes, at 14 days of exposure in gills and kidney erythrocytes. Significant elevation of cytotoxicity was detected after 2 and 14 days of exposure in gills erythrocytes and after 28 days-in peripheral blood erythrocytes. The amount of Cu, Cr, Pb and Cd accumulated in tissues was dependent upon duration of exposure; nuclear buds, 8-shaped nuclei frequencies also were dependent upon duration of exposure. This study indicates that metals at low levels when existing in mixture causes significant geno-cytotoxicity responses and metals bioaccumulation in salmon.

Investigation of the 66Zn(p,2pn) 64Cu and 68Zn(p,x) 64Cu nuclear processes up to 100 MeV: Production of 64Cu

NASA Astrophysics Data System (ADS)

Szelecsényi, F.; Steyn, G. F.; Kovács, Z.; Vermeulen, C.; van der Meulen, N. P.; Dolley, S. G.; van der Walt, T. N.; Suzuki, K.; Mukai, K.

2005-11-01

Cross-sections of the 66Zn(p,2pn)64Cu and 68Zn(p,x)64Cu nuclear processes were measured on highly enriched zinc targets using the stacked-foil activation technique up to 100 MeV. The new cross-sections were compared to literature data. The optimum energy range for production of 64Cu was found to be 70 → 35 MeV on 66Zn and 37 → 20 MeV on 68Zn. The thick-target yields were determined as 777 MBq/μAh (21.0 mCi/μAh) and 185 MBq/μAh (5.0 mCi/μAh), respectively. The yields of the longer-lived contaminant copper radioisotopes (i.e. 61Cu when using 66Zn as target material and both 61Cu and 67Cu in the case of 68Zn target material) were also calculated. The results obtained from the present study indicate that both reactions are suited for the production of 64Cu at a medium energy cyclotron. The optimum energy ranges are also complementary therefore the potential to utilize tandem targetry exists.

Optimization of Cu-Zn Massive Sulphide Flotation by Selective Reagents

NASA Astrophysics Data System (ADS)

Soltani, F.; Koleini, S. M. J.; Abdollahy, M.

2014-10-01

Selective floatation of base metal sulphide minerals can be achieved by using selective reagents. Sequential floatation of chalcopyrite-sphalerite from Taknar (Iran) massive sulphide ore with 3.5 % Zn and 1.26 % Cu was studied. D-optimal design of response surface methodology was used. Four mixed collector types (Aer238 + SIPX, Aero3477 + SIPX, TC1000 + SIPX and X231 + SIPX), two depressant systems (CuCN-ZnSO4 and dextrin-ZnSO4), pH and ZnSO4 dosage were considered as operational factors in the first stage of flotation. Different conditions of pH, CuSO4 dosage and SIPX dosage were studied for sphalerite flotation from first stage tailings. Aero238 + SIPX induced better selectivity for chalcopyrite against pyrite and sphalerite. Dextrin-ZnSO4 was as effective as CuCN-ZnSO4 in sphalerite-pyrite depression. Under optimum conditions, Cu recovery, Zn recovery and pyrite content in Cu concentrate were 88.99, 33.49 and 1.34 % by using Aero238 + SIPX as mixed collector, CuCN-ZnSO4 as depressant system, at ZnSO4 dosage of 200 g/t and pH 10.54. When CuCN was used at the first stage, CuSO4 consumption increased and Zn recovery decreased during the second stage. Maximum Zn recovery was 72.19 % by using 343.66 g/t of CuSO4, 22.22 g/t of SIPX and pH 9.99 at the second stage.

Genesis of the Assif El Mal Zn-Pb (Cu, Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural, mineralogical, and geochemical evidence

USGS Publications Warehouse

Bouabdellah, M.; Beaudoin, G.; Leach, D.L.; Grandia, F.; Cardellach, E.

2009-01-01

The Assif El Mal Zn-Pb (Cu-Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn-Pb (Cu-Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid-vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit Th mean values ranging from 104??C to 198??C. Final ice-melting temperatures range from -8.1??C to -12.8??C, corresponding to salinities of ???15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75??C to 150??C. The ??18O and ??D fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low ??13CVPDB values ranging from -7.5??? to -7.7??? indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn-Pb (Cu-Ag) veins. The calculated ??34SH2S values for reduced sulfur (22.5??? to 24.3???) are most likely from reduction of SO42- in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO2 which ultimately led to precipitation of saddle dolomite with

Assessment of oxidative stress and bioaccumulation of the metals Cu, Fe, Zn, Pb, Cd in the polychaete Perinereis gualpensis from estuaries of central Chile.

PubMed

Gaete, Hernán; Álvarez, Manuel; Lobos, Gabriela; Soto, Eulogio; Jara-Gutiérrez, Carlos

2017-11-01

The estuaries of the Aconcagua and Maipo Rivers of central Chile are receptors of residues that contain metals from anthropic activities including agriculture, mining and smelters, which have different levels in the two basins. This study postulates that the exposition to metals is different in the two estuaries and that their sediments contain bioavailable chemical agents that produce oxidative stress. The aim of the study was to evaluate the effect of estuarine sediments on the polychaete Perinereis gualpensis using oxidative stress biomarkers and to determine the metal concentrations in sediments and their accumulation in P. gualpensis. Sediments and organisms were collected in December 2015 and January 2016 in the estuaries. The Catapilco estuary was used as control, since its basin has little anthropic activity. The metal concentrations of Fe Cu, Pb, Zn and Cd were determined in tissues of the organisms and in sediments. The granulometry, conductivity, redox potential, pH and organic matter in sediments were determined, as well as catalase activity and lipid peroxidation. The results show that the concentrations of metals in sediments were higher in the estuary of the Aconcagua River: Cu: 48 ± 2μgg -1 ; Fe: 154 ± 19mgg -1 , Pb: 20 ± 3μgg -1 and Zn: 143 ± 20μgg -1 . In tissues, Pb and Fe were higher in the estuary of the Maipo River, while Cd was detected only in the Catapilco River mouth. Catalase activity was greater in the estuary of the Aconcagua River and lipid peroxidation in the estuary of the Catapilco River. Significant regressions were found between biomarkers of oxidative stress and metal concentrations in tissues of P. gualpensis. In conclusion, the sediments of the studied estuaries contain bioavailable chemical agents that provoke oxidative stress in P. gualpensis, which may be a risk for the benthic communities of these ecosystems. This species is proposed to monitor metals bioavailability and oxidative stress in estuarine sediments

A two-step leaching method designed based on chemical fraction distribution of the heavy metals for selective leaching of Cd, Zn, Cu, and Pb from metallurgical sludge.

PubMed

Wang, Fen; Yu, Junxia; Xiong, Wanli; Xu, Yuanlai; Chi, Ru-An

2018-01-01

For selective leaching and highly effective recovery of heavy metals from a metallurgical sludge, a two-step leaching method was designed based on the distribution analysis of the chemical fractions of the loaded heavy metal. Hydrochloric acid (HCl) was used as a leaching agent in the first step to leach the relatively labile heavy metals and then ethylenediamine tetraacetic acid (EDTA) was applied to leach the residual metals according to their different fractional distribution. Using the two-step leaching method, 82.89% of Cd, 55.73% of Zn, 10.85% of Cu, and 0.25% of Pb were leached in the first step by 0.7 M HCl at a contact time of 240 min, and the leaching efficiencies for Cd, Zn, Cu, and Pb were elevated up to 99.76, 91.41, 71.85, and 94.06%, by subsequent treatment with 0.2 M EDTA at 480 min, respectively. Furthermore, HCl leaching induced fractional redistribution, which might increase the mobility of the remaining metals and then facilitate the following metal removal by EDTA. The facilitation was further confirmed by the comparison to the one-step leaching method with single HCl or single EDTA, respectively. These results suggested that the designed two-step leaching method by HCl and EDTA could be used for selective leaching and effective recovery of heavy metals from the metallurgical sludge or heavy metal-contaminated solid media.

Temporal Variation and Ecological Risk Assessment of Metals in Soil Nearby a Pb⁻Zn Mine in Southern China.

PubMed

Cao, Congcong; Wang, Li; Li, Hairong; Wei, Binggan; Yang, Linsheng

2018-05-09

Metal contamination in soil from tailings induces risks for the ecosystem and for humans. In this study, the concentrations and ecological risks of Cd, Cu, Pb, and Zn in soil contaminated by a tailing from Yangshuo (YS) lead and zinc (Pb⁻Zn) mine, which collapsed for more than 40 years, were determined in 2015. The mean concentrations of Zn, Pb, Cu, and Cd were 1301.79, 768.41, 82.60, and 4.82 mg/kg, respectively, which, with years of remediation activities, decreased by 66.9%, 61.7%, 65.4%, and 65.3% since 1986, but still exceed the national standards. From 1986 to 2015, soil pH increased significantly, with available concentrations of Zn, Pb, Cu and Cd decreasing by 13%, 81%, 77%, and 67%, respectively, and potential ecological risk indexes ( E r ) of the determined metals decreasing by more than 60%. Horizontally, total contents and percentages of available concentrations of Zn, Pb, Cu, and Cd decreased with the distance from the tailing heap in SD village, while pH values showed the reverse pattern. Vertically, Zn and Cd, Pb, and Cu showed similar vertical distribution patterns in the soil profiles. There was a slight downward migration for the determined metals in soil of M and H area and the mobility was in the order of Cd > Zn > Pb > Cu. It can be concluded that although concentrations and ecological risks of Cd, Cu, Pb, and Zn in soil decreased significantly, SD village is still a high risk area, and the priority pollutant is Cd.

Temporal Variation and Ecological Risk Assessment of Metals in Soil Nearby a Pb–Zn Mine in Southern China

PubMed Central

Cao, Congcong; Wang, Li; Li, Hairong; Wei, Binggan

2018-01-01

Metal contamination in soil from tailings induces risks for the ecosystem and for humans. In this study, the concentrations and ecological risks of Cd, Cu, Pb, and Zn in soil contaminated by a tailing from Yangshuo (YS) lead and zinc (Pb–Zn) mine, which collapsed for more than 40 years, were determined in 2015. The mean concentrations of Zn, Pb, Cu, and Cd were 1301.79, 768.41, 82.60, and 4.82 mg/kg, respectively, which, with years of remediation activities, decreased by 66.9%, 61.7%, 65.4%, and 65.3% since 1986, but still exceed the national standards. From 1986 to 2015, soil pH increased significantly, with available concentrations of Zn, Pb, Cu and Cd decreasing by 13%, 81%, 77%, and 67%, respectively, and potential ecological risk indexes (Er) of the determined metals decreasing by more than 60%. Horizontally, total contents and percentages of available concentrations of Zn, Pb, Cu, and Cd decreased with the distance from the tailing heap in SD village, while pH values showed the reverse pattern. Vertically, Zn and Cd, Pb, and Cu showed similar vertical distribution patterns in the soil profiles. There was a slight downward migration for the determined metals in soil of M and H area and the mobility was in the order of Cd > Zn > Pb > Cu. It can be concluded that although concentrations and ecological risks of Cd, Cu, Pb, and Zn in soil decreased significantly, SD village is still a high risk area, and the priority pollutant is Cd. PMID:29747376

[Stabilization Treatment of Pb and Zn in Contaminated Soils and Mechanism Studies].

PubMed

Xie, Wei-qiang; Li, Xiao-mingi; Chen, Can; Chen, Xun-feng; Zhong, Yu; Zhong, Zhen-yu; Wan, Yong; Wang, Yan

2015-12-01

In the present work, the combined application of potassium dihydrogen phosphate, quick lime and potassium chloride was used to immobilize the Pb and Zn in contaminated soils. The efficiency of the process was evaluated through leaching tests and Tessier sequential extraction procedure. The mechanism of stabilization was analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to reveal the mechanism of stabilization. The results showed that the stabilizing efficiency of Pb contaminated soils was above 80% and the leaching concentrations of Pb, Zn were far below the threshold when the ratio of exogenous P and soil (mol · mol⁻¹) was 2:1-4: 1, the dosing ratio of CaO was 0.1%-0.5% ( mass fraction) and the dosage of potassium chloride was 0.02-0. 04 mol. Meanwhile, Pb and Zn in soil were transformed from the exchangeable fraction into residual fraction, which implied that the migration of Pb, Zn in soil could be confined by the stabilization treatment. XRD and SEM analysis revealed that Ca-P-Pb precipitation, lead orthophosphate [PbHP0₄, Pb₃ (PO₄)₂], pyromorphite (Pb-PO₄-Cl/OH) and mixed heavy metal deposits (Fe-PO₄- Ca-Pb-Zn-OH) could be formed after solidification/stabilization in which Pb and Zn could be wrapped up to form a solidified composition and to prevent leaching.

Mobility and fractionation of Fe, Pb and Zn in river sediments from a silver and base-metals mining area: Taxco, México.

PubMed

Espinosa, E; Armienta, M A

2007-08-01

The impact of mining wastes on both the concentration and environmental mobility of Zn, Pb and Fe was studied in a shallow river. The studied tributary of the Taxco river is located south of the historical Ag, Zn, Cu and Pb mining area of Taxco, about 150 km south of México City. Methodology included total concentration determinations and sequential extraction analyses of the operational defined fractions of sediments. Results indicated that Fe, Pb and Zn concentrations are up to 5, 100 and 390 times respectively, greater than regional background concentrations. Higher contents of Pb and Zn were observed in the rainy season versus the dry season, whereas Fe was lower in the rainy season. Zinc and lead increased downflow in the dry season, and did not show any trend during the rainy season. Speciation showed that Zn was mainly linked to the carbonatic fraction (25-39%), to the hydrous Fe/Mn oxides fraction (15-25%) and to the organic matter and sulfide fraction (14-48%); lead was mainly associated to the hydrous Fe/Mn oxides (49-59%) and residual (22-39%) fractions; finally, iron was contained mainly in the residual (65-78%) and the hydrous Fe/Mn oxides fraction (15%). Mobility decreased according to the relation: Zn > Pb > Fe. Sediments were classified as strongly polluted in zinc, strongly to very strongly polluted in Pb, and moderately to strongly polluted in iron. However, a low proportion of metals in the exchangeable fractions, indicates low bioavailability. Limestone presence played a very important role on Zn and Pb fractionation and environmental mobility. Results show the importance of including geological background in river pollution studies.

Elastocaloric effect in CuAlZn and CuAlMn shape memory alloys under compression

PubMed Central

Qian, Suxin; Wang, Yi; Pillsbury, Thomas E.; Hada, Yoshiharu; Yamaguchi, Yuki; Fujimoto, Kenjiro; Hwang, Yunho; Radermacher, Reinhard; Cui, Jun; Yuki, Yoji; Toyotake, Koutaro; Takeuchi, Ichiro

2016-01-01

This paper reports the elastocaloric effect of two Cu-based shape memory alloys: Cu68Al16Zn16 (CuAlZn) and Cu73Al15Mn12 (CuAlMn), under compression at ambient temperature. The compression tests were conducted at two different rates to approach isothermal and adiabatic conditions. Upon unloading at a strain rate of 0.1 s−1 (adiabatic condition) from 4% strain, the highest adiabatic temperature changes (ΔTad) of 4.0 K for CuAlZn and 3.9 K for CuAlMn were obtained. The maximum stress and hysteresis at each strain were compared. The stress at the maximum recoverable strain of 4.0% for CuAlMn was 120 MPa, which is 70% smaller than that of CuAlZn. A smaller hysteresis for the CuAlMn alloy was also obtained, about 70% less compared with the CuAlZn alloy. The latent heat, determined by differential scanning calorimetry, was 4.3 J g−1 for the CuAlZn alloy and 5.0 J g−1 for the CuAlMn alloy. Potential coefficients of performance (COPmat) for these two alloys were calculated based on their physical properties of measured latent heat and hysteresis, and a COPmat of approximately 13.3 for CuAlMn was obtained. This article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’. PMID:27402936

Room temperature ferromagnetism in Cu doped ZnO

NASA Astrophysics Data System (ADS)

Ali, Nasir; Singh, Budhi; Khan, Zaheer Ahmed; Ghosh, Subhasis

2018-05-01

We report the room temperature ferromagnetism in 2% Cu doped ZnO films grown by RF magnetron sputtering in different argon and oxygen partial pressure. X-ray photoelectron spectroscopy was used to ascertain the oxidation states of Cu in ZnO. The presence of defects within Cu-doped ZnO films can be revealed by electron paramagnetic resonance. It has been observed that saturated magnetic moment increase as we increase the zinc vacancies during deposition.

Metallogeny of the Paramillos de Uspallata Pb-Zn-Ag vein deposit in the Cuyo Rift Basin, Argentina

NASA Astrophysics Data System (ADS)

Rubinstein, Nora A.; Carrasquero, Silvia I.; Gómez, Anabel L. R.; Ricchetti, Ana P. Orellano; D'Annunzio, María C.

2018-05-01

The Paramillos de Uspallata deposit, previously considered as genetically linked to a Miocene porphyry deposit, is located in the Mesozoic Cuyo Basin, which was formed during the beginning of the break-up of Gondwana. In the present study, both previous information and new geological, mineralogical, and isotopic data allowed outlining a new descriptive model for this deposit. Stratigraphic and structural controls allowed considering this deposit as contemporaneous with the Mesozoic rifting, with the mineralization resulting from a Pb-Zn stage followed by an Ag-Cu-Pb stage. The hydrothermal fluids were found to have low temperature and low to moderate salinity, and to result from the mixing between metamorphic and meteoric fluids, with the lead sourced by the igneous Paleozoic basement and the sulfur partly derived from a magmatic source. These characteristics allow describing Paramillos de Uspallata as Pb-Zn-Ag veins hosted in clastic sedimentary sequences genetically linked to a rift basin and redefining it as detachment-related mineralization.

A Stable Plasmonic Cu@Cu2 O/ZnO Heterojunction for Enhanced Photocatalytic Hydrogen Generation.

PubMed

Lou, Yongbing; Zhang, Yake; Cheng, Lin; Chen, Jinxi; Zhao, Yixin

2018-05-09

The localized surface plasmon resonance (LSPR) effect has been widely utilized in photocatalysis, but most reported LSPR materials are based on noble metals of gold or silver with high chemical stability. Plasmonic copper nanoparticles that exhibit an LSPR absorbance at 600 nm are promising for many applications, such as photocatalysis. Unfortunately, plasmonic copper nanoparticles are affected by serious surface oxidation in air. Herein, a novel lollipop-shaped Cu@Cu 2 O/ZnO heterojunction nanostructure was designed, for the first time, to stabilize the plasmonic Cu core by decorating Cu@Cu 2 O core-shell structures with ZnO nanorods. This Cu@Cu 2 O/ZnO nanostructure exhibited significantly enhanced stability than that of regular Cu@Cu 2 O, which accounted for the remarkably enhanced photocatalytic H 2 evolution rate through water splitting, relative to pristine ZnO nanorods, over an extended wavelength range due to the plasmonic Cu core. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnCuInS/ZnSe/ZnS quantum dot-based downconversion light-emitting diodes and their thermal effect

DOE PAGES

Liu, Wenyan; Zhang, Yu; Wang, Dan; ...

2015-08-13

The quantum dot-based light-emitting diodes (QD-LEDs) were fabricated using blue GaN chips and red-, yellow-, and green-emitting ZnCuInS/ZnSe/ZnS QDs. The power efficiencies were measured as 14.0 lm/W for red, 47.1 lm/W for yellow, and 62.4 lm/W for green LEDs at 2.6 V. The temperature effect of ZnCuInS/ZnSe/ZnS QDs on these LEDs was investigated using CIE chromaticity coordinates, spectral wavelength, full width at half-maximum (FWHM) and power efficiencies (PE). The thermal quenching induced by the increased surface temperature of the device was confirmed to be one of the important factors to decrease power efficiencies while the CIE chromaticity coordinates changed littlemore » due to the low emission temperature coefficients of 0.022, 0.050 and 0.068 nm/°C for red-, yellow- and green-emitting ZnCuInS/ZnSe/ZnS QDs. Lastly this indicates that ZnCuInS/ZnSe/ZnS QDs are more suitable for down-conversion LEDs compared to CdSe QDs.« less

Heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in seven fish species in relation to fish size and location along the Yangtze River.

PubMed

Yi, Yu-Jun; Zhang, Shang-Hong

2012-11-01

The objective of this paper is to assess the regulation of the accumulation of heavy metals in the aquatic environment and different fish species. Water and fish samples were collected from upper to lower reaches of the Yangtze River. The heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in the muscle tissue of seven fishes were measured. Additionally, the relationships between heavy metal concentrations in fish tissue and fish size (length and weight), condition factor, water layer distribution, and trophic level were investigated. Metal concentrations (milligrams per kilogram wet weight) were found to be distributed differently among different fish species. The highest concentrations of Cu (1.22 mg/kg) and Zn (7.55 mg/kg) were measured in Pelteobagrus fulvidraco, the highest concentrations of Cd (0.115 mg/kg) and Hg (0.0304 mg/kg) were measured in Silurus asotus, and the highest concentrations of Pb (0.811 mg/kg) and Cr (0.239 mg/kg) were measured in Carassius auratus and Cyprinus carpio. A positive relationship was found between fish size and metal level in most cases. The variance of the relationships may be the result of differences in habitat, swimming behavior, and metabolic activity. In this study, fishes living in the lower water layer and river bottom had higher metals concentrations than in upper and middle layers. Benthic carnivorous and euryphagous fish had higher metals concentrations than phytoplankton and herbivorous fish. Generally, fish caught from the lower reach had higher metals concentrations than those from the upper reach. Cadmium and lead concentrations in several fishes exceeded the permissible food consumption limits, this should be considered to be an important warning signal.

Bioleaching mechanism of Zn, Pb, In, Ag, Cd and As from Pb/Zn smelting slag by autotrophic bacteria.

PubMed

Wang, Jia; Huang, Qifei; Li, Ting; Xin, Baoping; Chen, Shi; Guo, Xingming; Liu, Changhao; Li, Yuping

2015-08-15

A few studies have focused on release of valuable/toxic metals from Pb/Zn smelting slag by heterotrophic bioleaching using expensive yeast extract as an energy source. The high leaching cost greatly limits the practical potential of the method. In this work, autotrophic bioleaching using cheap sulfur or/and pyrite as energy matter was firstly applied to tackle the smelting slag and the bioleaching mechanisms were explained. The results indicated autotrophic bioleaching can solubilize valuable/toxic metals from slag, yielding maximum extraction efficiencies of 90% for Zn, 86% for Cd and 71% for In, although the extraction efficiencies of Pb, As and Ag were poor. The bioleaching performance of Zn, Cd and Pb was independent of leaching system, and leaching mechanism was acid dissolution. A maximum efficiency of 25% for As was achieved by acid dissolution in sulfursulfur oxidizing bacteria (S-SOB), but the formation of FeAsO4 reduced extraction efficiency in mixed energy source - mixed culture (MS-MC). Combined works of acid dissolution and Fe(3+) oxidation in MS-MC was responsible for the highest extraction efficiency of 71% for In. Ag was present in the slag as refractory AgPb4(AsO4)3 and AgFe2S3, so extraction did not occur. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhanced thermoelectric performance through grain boundary engineering in quaternary chalcogenide Cu2ZnSnSe4

NASA Astrophysics Data System (ADS)

Zhu, Yingcai; Liu, Yong; Tan, Xing; Ren, Guangkun; Yu, Meijuan; Hu, Tiandou; Marcelli, Augusto; Xu, Wei

2018-04-01

Quaternary chalcogenide Cu2ZnSnSe4 (CZTSe) is a promising wide band-gap p-type thermoelectric material. The structure and thermoelectric properties of lead substituted Cu2ZnSn1-xPbxSe4 are investigated. Lead primarily exists in the framework of PbSe as demonstrated by x-ray diffraction and calculation of x-ray absorption near-edge structure spectroscopy. The second phase distributes at the boundaries of CZTSe with thickness in several hundreds of nanometer. With appropriate grain boundary engineering, the enhancement of power factor and a decrease of thermal conductivity can be achieved simultaneously. As a result, a maximum figure of merit zT of 0.45 is obtained for the sample with x=0.02 at 723K.

Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

NASA Astrophysics Data System (ADS)

Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

2016-09-01

With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

ZnTe Alloying Effect on Enhanced Thermoelectric Properties of p-Type PbTe.

PubMed

Ahn, Kyunghan; Shin, Hocheol; Im, Jino; Park, Sang Hyun; Chung, In

2017-02-01

We investigate the effect of ZnTe incorporation on PbTe to enhance thermoelectric performance. We report structural, microscopic, and spectroscopic characterizations, ab initio theoretical calculations, and thermoelectric transport properties of Pb 0.985 Na 0.015 Te-x% ZnTe (x = 0, 1, 2, 4). We find that the solid solubility limit of ZnTe in PbTe is less than 1 mol %. The introduction of 2% ZnTe in p-type Pb 0.985 Na 0.015 Te reduces the lattice thermal conductivity through the ZnTe precipitates at the microscale. Consequently, a maximum thermoelectric figure of merit (ZT) of 1.73 at 700 K is achieved for the spark plasma-sintered Pb 0.985 Na 0.015 Te-2% ZnTe, which arises from a decreased lattice thermal conductivity of ∼0.69 W m -1 K -1 at ∼700 K in comparison with Pb 0.985 Na 0.015 Te.

Cu-Doped ZnO Thin Films Grown by Co-deposition Using Pulsed Laser Deposition for ZnO and Radio Frequency Sputtering for Cu

NASA Astrophysics Data System (ADS)

Shin, Hyun Wook; Son, Jong Yeog

2018-05-01

Cu-doped ZnO (CZO) thin films were fabricated on single-crystalline (0001) Al2O3 substrates by co-deposition using pulsed laser deposition for ZnO and radio frequency sputtering for Cu. CZO thin films with 0-20% molar concentrations are obtained by adjusting the deposition rates of ZnO and Cu. The CZO thin films exhibit room temperature ferromagnetism, and CZO with 5% Cu molar concentration has maximum remanent magnetization, which is consistent with theoretical results.

Heavy metals pollution and pb isotopic signatures in surface sediments collected from Bohai Bay, North China.

PubMed

Gao, Bo; Lu, Jin; Hao, Hong; Yin, Shuhua; Yu, Xiao; Wang, Qiwen; Sun, Ke

2014-01-01

To investigate the characteristics and potential sources of heavy metals pollution, surface sediments collected from Bohai Bay, North China, were analyzed for the selected metals (Cd, Cr, Cu, Ni, Pb, and Zn). The Geoaccumulation Index was used to assess the level of heavy metal pollution. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of Cd, Cr, Cu, Ni, Pb, and Zn were 0.15, 79.73, 28.70, 36.56, 25.63, and 72.83 mg/kg, respectively. The mean concentrations of the studied metals were slightly higher than the background values. However, the heavy metals concentrations in surface sediments in Bohai Bay were below the other important bays or estuaries in China. The assessment by Geoaccumulation Index indicated that Cr, Zn, and Cd were classified as "the unpolluted" level, while Ni, Cu, and Pb were ranked as "unpolluted to moderately polluted" level. The order of pollution level of heavy metals was: Pb > Ni > Cu > Cr > Zn > Cd. The Pb isotopic ratios in surface sediments varied from 1.159 to 1.185 for (206)Pb/(207)Pb and from 2.456 to 2.482 for (208)Pb/(207)Pb. Compared with Pb isotopic radios in other sources, Pb contaminations in the surface sediments of Bohai Bay may be controlled by the mix process of coal combustion, aerosol particles deposition, and natural sources.

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al 2O 3) catalysts for carbon dioxide (CO 2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. Here, we report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO andmore » allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. These results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.« less

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts

DOE PAGES

Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.; ...

2017-03-23

The active sites over commercial copper/zinc oxide/aluminum oxide (Cu/ZnO/Al 2O 3) catalysts for carbon dioxide (CO 2) hydrogenation to methanol, the Zn-Cu bimetallic sites or ZnO-Cu interfacial sites, have recently been the subject of intense debate. Here, we report a direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis. By combining x-ray photoemission spectroscopy, density functional theory, and kinetic Monte Carlo simulations, we can identify and characterize the reactivity of each catalyst. Both experimental and theoretical results agree that ZnCu undergoes surface oxidation under the reaction conditions so that surface Zn transforms into ZnO andmore » allows ZnCu to reach the activity of ZnO/Cu with the same Zn coverage. These results highlight a synergy of Cu and ZnO at the interface that facilitates methanol synthesis via formate intermediates.« less

ZnO/Cu(InGa)Se.sub.2 solar cells prepared by vapor phase Zn doping

DOEpatents

Ramanathan, Kannan; Hasoon, Falah S.; Asher, Sarah E.; Dolan, James; Keane, James C.

2007-02-20

A process for making a thin film ZnO/Cu(InGa)Se.sub.2 solar cell without depositing a buffer layer and by Zn doping from a vapor phase, comprising: depositing Cu(InGa)Se.sub.2 layer on a metal back contact deposited on a glass substrate; heating the Cu(InGa)Se.sub.2 layer on the metal back contact on the glass substrate to a temperature range between about 100.degree. C. to about 250.degree. C.; subjecting the heated layer of Cu(InGa)Se.sub.2 to an evaporant species from a Zn compound; and sputter depositing ZnO on the Zn compound evaporant species treated layer of Cu(InGa)Se.sub.2.

Electrodeposition of CuZn Alloys from the Non-Cyanide Alkaline Baths

NASA Astrophysics Data System (ADS)

Li, Minggang; Wei, Guoying; Hu, Shuangshuang; Xu, Shuhan; Yang, Yejiong; Miao, Qinfang

2015-10-01

Effect of copper sulfate on CuZn alloys electroplating from non-cyanide baths are investigated by different electrochemical methods. Cyclic voltammetry and current transient measurements are used to characterize the CuZn alloys electroplating system in order to analyze the nucleation and growth mechanism. The reduction of Cu and CuZn alloy on sheet iron substrates shows an instantaneous nucleation process. However, the reduction of Zn on sheet iron substrates shows a progressive nucleation process. The structure and surface morphology of CuZn alloys are analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The morphology of CuZn alloys obtained with 50 g L-1 copper sulfate presents a smooth and compact deposit and the size of crystal particle is uniform.

Novel dimeric interface and electrostatic recognition in bacterial Cu,Zn superoxide dismutase

PubMed Central

Bourne, Yves; Redford, Susan M.; Steinman, Howard M.; Lepock, James R.; Tainer, John A.; Getzoff, Elizabeth D.

1996-01-01

Eukaryotic Cu,Zn superoxide dismutases (CuZnSODs) are antioxidant enzymes remarkable for their unusually stable β-barrel fold and dimer assembly, diffusion-limited catalysis, and electrostatic guidance of their free radical substrate. Point mutations of CuZnSOD cause the fatal human neurodegenerative disease amyotrophic lateral sclerosis. We determined and analyzed the first crystallographic structure (to our knowledge) for CuZnSOD from a prokaryote, Photobacterium leiognathi, a luminescent symbiont of Leiognathid fish. This structure, exemplifying prokaryotic CuZnSODs, shares the active-site ligand geometry and the topology of the Greek key β-barrel common to the eukaryotic CuZnSODs. However, the β-barrel elements recruited to form the dimer interface, the strategy used to forge the channel for electrostatic recognition of superoxide radical, and the connectivity of the intrasubunit disulfide bond in P. leiognathi CuZnSOD are discrete and strikingly dissimilar from those highly conserved in eukaryotic CuZnSODs. This new CuZnSOD structure broadens our understanding of structural features necessary and sufficient for CuZnSOD activity, highlights a hitherto unrecognized adaptability of the Greek key β-barrel building block in evolution, and reveals that prokaryotic and eukaryotic enzymes diverged from one primordial CuZnSOD and then converged to distinct dimeric enzymes with electrostatic substrate guidance. PMID:8917495

A rapid, partial leach and organic separation for the sensitive determination of Ag, Bi, Cd, Cu, Mo, Pb, Sb, and Zn in surface geologic materials by flame atomic absorption

USGS Publications Warehouse

Viets, J.G.; Clark, J.R.; Campbell, W.L.

1984-01-01

A solution of dilute hydrochloric acid, ascorbic acid, and potassium iodide has been found to dissolve weakly bound metals in soils, stream sediments, and oxidized rocks. Silver, Bi, Cd, Cu, Mo, Pb, Sb, and Zn are selectively extracted from this solution by a mixture of Aliquat 336 (tricaprylyl methyl ammonium chloride) and MIBK (methyl isobutyl ketone). Because potentially interfering major and minor elements do not extract, the organic separation allows interference-free determinations of Ag and Cd to the 0.05 ppm level, Mo, Cu, and Zn to 0.5 ppm, and Bi, Pb, and Sb to 1 ppm in the sample using flame atomic absorption spectroscopy. The analytical absorbance values of the organic solution used in the proposed method are generally enhanced more than threefold as compared to aqueous solutions, due to more efficient atomization and burning characteristics. The leaching and extraction procedures are extremely rapid; as many as 100 samples may be analyzed per day, yielding 800 determinations, and the technique is adaptable to field use. The proposed method was compared to total digestion methods for geochemical reference samples as well as soils and stream sediments from mineralized and unmineralized areas. The partial leach showed better anomaly contrasts than did total digestions. Because the proposed method is very rapid and is sensitive to pathfinder elements for several types of ore deposits, it should be useful for reconnaissance surveys for concealed deposits. ?? 1984.

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

DOE PAGES

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan; ...

2017-08-21

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

Hydrogenation of CO 2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palomino, Robert M.; Ramirez, Pedro J.; Liu, Zongyuan

The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO 2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making themore » supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO 2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO 2 hydrogenation reaction. However, reaction with CO 2 oxidized the zinc, enhancing its stability over the copper substrates.« less

Cyclotron production of {sup 61}Cu using natural Zn and enriched {sup 64}Zn targets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asad, A. H.; Smith, S. V.; Chan, S.

2012-12-19

Copper-61 ({sup 61}Cu) shares with {sup 64}Cu certain advantages for PET diagnostic imaging, but has a shorter half-life (3.4hr vs. 12.7hr) and a greater probability of positron production per disintegration (61% vs. 17.9%). One important application is for in vivo imaging of hypoxic tissue. In this study {sup 61}Cu was produced using the {sup 64}Zn(p,{alpha}){sup 61}Cu reaction on natural Zn or enriched {sup 64}Zn targets. The enriched {sup 64}Zn (99.82%) was electroplated onto high purity gold or silver foils or onto thin Al discs. A typical target bombardment used 30{mu}A; at 11.7, 14.5 or 17.6MeV over 30-60min. The {sup 61}Cumore » (radiochemical purity of >95%) was separated using a combination of cation and anion exchange columns. The {sup 64}Zn target material was recovered after each run, for re-use. In a direct comparison with enriched {sup 64}Zn-target results, {sup 61}Cu production using the cheaper {sup nat}Zn target proved to be an effective alternative.« less

The giant Upper Yangtze Pb-Zn province in SW China: Reviews, new advances and a new genetic model

NASA Astrophysics Data System (ADS)

Zhou, Jia-Xi; Xiang, Zhen-Zhong; Zhou, Mei-Fu; Feng, Yue-Xing; Luo, Kai; Huang, Zhi-Long; Wu, Tao

2018-04-01

western Yangtze Block. The change of tectonic regimes from extension to compression after eruption of basalts of the ELIP, and then to extension during Early Mesozoic, facilitated extraction, migration, and excretion of ore-forming metals and associated fluids. Mixing of fluids and reduction geochemical barrier activated TSR, causing cyclical carbonate dissolution, CO2 degassing and recrystallization (namely carbonate buffer). All these processes triggered continuous precipitation of huge amounts of hydrothermal minerals. Underplating and eruption of ELIP basalts provided heat flow, fluids and volatiles, whereas the basalts acted as an impermeable and protective layer, and even as ore-hosting rocks. These Pb-Zn deposits have spatial and genetic association with igneous activities of the ELIP, and are characterized by high ore grades (>10 wt% Pb + Zn), high concentrations of associated metals (e.g. Cu, Ag, Ge, and Cd), and medium-low temperatures (usually < 300 °C) and salinities (commonly < 20 wt% NaCl equiv.), all of which are significantly different from those of typical Mississippi Valley-type (MVT) deposits. Hence, the carbonate-hosted epigenetic Pb-Zn deposits in the Upper Yangtze metallogenic province representing to a new type of Pb-Zn deposits that are hosted in platform carbonate sequences and formed within compressional zones of passive margin tectonic settings.

Fractionation and mobility of Cu, Fe, Mn, Pb and Zn in the road dust retained on noise barriers along expressway - a potential tool for determining the effects of driving conditions on speciation of emitted particulate metals.

PubMed

Świetilik, Ryszard; Trojanowska, Marzena; Strzelecka, Monika; Bocho-Janiszewska, Anita

2015-01-01

Road dust (RD) retained on noise barriers was used as a monitor of emission of traffic-related metals from expressway. By using SEM/EDX analysis it has been revealed that the main components of this particulate were irregular fine aggregates and tire debris with a ragged porous structure and with inclusions derived from the road surface. The results of chemical fractionation showed that driving conditions influence strongly a distribution pattern of Cu, whereas the atmospheric corrosion process affects a distribution pattern of Zn. The distribution pattern of Cu originating only from vehicle braking emission was “isolated” from the distribution pattern of road traffic copper. The predicted comparative mobilities of the emitted metals form the order: Zn > Cu ≈ Mn > Pb > Fe. The high mobility of zinc (K = 0.61)may create a current inhalation hazard and may be a source of future environmental hazard in the areas adjacent to heavily trafficked roads.

Compositional ratio effect on the surface characteristics of CuZn thin films

NASA Astrophysics Data System (ADS)

Choi, Ahrom; Park, Juyun; Kang, Yujin; Lee, Seokhee; Kang, Yong-Cheol

2018-05-01

CuZn thin films were fabricated by RF co-sputtering method on p-type Si(100) wafer with various RF powers applied on metallic Cu and Zn targets. This paper aimed to determine the morphological, chemical, and electrical properties of the deposited CuZn thin films by utilizing a surface profiler, atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), UV photoelectron spectroscopy (UPS), and a 4-point probe. The thickness of the thin films was fixed at 200 ± 8 nm and the roughness of the thin films containing Cu was smaller than pure Zn thin films. XRD studies confirmed that the preferred phase changed, and this tendency is dependent on the ratio of Cu to Zn. AES spectra indicate that the obtained thin films consisted of Cu and Zn. The high resolution XPS spectra indicate that as the content of Cu increased, the intensities of Zn2+ decreased. The work function of CuZn thin films increased from 4.87 to 5.36 eV. The conductivity of CuZn alloy thin films was higher than pure metallic thin films.

Build-up and wash-off dynamics of atmospherically derived Cu, Pb, Zn and TSS in stormwater runoff as a function of meteorological characteristics.

PubMed

Murphy, Louise U; Cochrane, Thomas A; O'Sullivan, Aisling

2015-03-01

Atmospheric pollutants deposited on impermeable surfaces can be an important source of pollutants to stormwater runoff; however, modelling atmospheric pollutant loads in runoff has rarely been done, because of the challenges and uncertainties in monitoring their contribution. To overcome this, impermeable concrete boards (≈ 1m(2)) were deployed for 11 months in different locations within an urban area (industrial, residential and airside) throughout Christchurch, New Zealand, to capture spatially distributed atmospheric deposition loads in runoff over varying meteorological conditions. Runoff was analysed for total and dissolved Cu, Zn, Pb, and total suspended solids (TSS). Mixed-effect regression models were developed to simulate atmospheric pollutant loads in stormwater runoff. In addition, the models were used to explain the influence of different meteorological characteristics (e.g. antecedent dry days and rain depth) on pollutant build-up and wash-off dynamics. The models predicted approximately 53% to 69% of the variation in pollutant loads and were successful in predicting pollutant-load trends over time which can be useful for general stormwater planning processes. Results from the models illustrated the importance of antecedent dry days on pollutant build-up. Furthermore, results indicated that peak rainfall intensity and rain duration had a significant relationship with TSS and total Pb, whereas, rain depth had a significant relationship with total Cu and total Zn. This suggested that the pollutant speciation phase plays an important role in surface wash-off. Rain intensity and duration had a greater influence when the pollutants were predominantly in their particulate phase. Conversely, rain depth exerted a greater influence when a high fraction of the pollutants were predominantly in their dissolved phase. For all pollutants, the models were represented by a log-arctan relationship for pollutant build-up and a log-log relationship for pollutant wash

Mesozoic magmatism and timing of epigenetic Pb-Zn-Ag mineralization in the western Fortymile mining district, east-central Alaska: Zircon U-Pb geochronology, whole-rock geochemistry, and Pb isotopes

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Aleinkoff, J.N.; Day, W.C.; Mortensen, J.K.

2015-01-01

Epigenetic Pb-Zn-Ag ± Cu prospects in the western Fortymile district are spatially associated with splays of the northeast-trending Kechumstuk sinistral-normal fault zone and with ca. 68-66 Ma felsic intrusions and dikes. The similarity between Pb isotope compositions of feldspars from the Late Cretaceous igneous bodies and sulfides from the epithermal prospects suggests a Late Cretaceous age for most of the mineralization. Fluid flow along the faults undoubtedly played a major role in mineralization. We interpret displacement on the northeast-trending faults to be a far-field effect of dextral translation along Late Cretaceous plate-scale boundaries and faults that were roughly parallel to the subsequently developed Denali and Tintina fault systems, which currently bound the region.

Cryoprotective role of organic Zn and Cu supplementation in goats (Capra hircus) diet.

PubMed

Arangasamy, Arunachalam; Krishnaiah, Mayasula Venkata; Manohar, Narasimhaiah; Selvaraju, Sellappan; Rani, Guvvala Pushpa; Soren, Nira Manik; Reddy, Ippala Janardhan; Ravindra, Janivara Parameshwaraiah

2018-04-01

The current study focused on cryopreservation and assessment of characters of post-thaw semen of indigenous Osmanabadi bucks maintained with standard diet, supplemented with different concentrations of organic zinc (Zn), copper (Cu) or in combination, for a period of 180 days. The different doses of organic Zn and Cu were fed per kg DM basis, Zn groups (low: Zn20, medium: Zn40 and high: Zn60), Cu groups: (low: Cu12.5, medium: Cu25 and high: Cu37.5) and combination of Zn + Cu groups (low: Zn20 + Cu12.5, medium: Zn40 + Cu25 and high: Zn60 + Cu37.5) respectively. The control group bucks were maintained mainly on the basal diet without any additional mineral supplementation. Two hundred and forty (240) semen samples were collected from 40 bucks aged 11 months, through electro ejaculator method, processed and analysed for sperm quality parameters both at pre freeze and post-thaw stage. The semen samples were diluted in Tris egg yolk extender, cooled and equilibrated for 4 h at 5 °C, cryopreserved using programmable freezer (PLANER Kryo 360-1.7) and stored at -196 °C. The organic trace minerals (Zn, Cu and Zn + Cu) protected the spermatozoa against the cryoinjury and maintained higher post-thaw semen parameters except in high Zn group. Additional feeding of organic Cu and Zn to bucks had a protective role and resulted in higher sperm liveability, plasma membrane and acrosome integrities, motility and velocity and reduced oxidative stress in supplemented goats (P < 0.05). Copyright © 2018 Elsevier Inc. All rights reserved.

Metallogeny of precious and base metal mineralization in the Murchison Greenstone Belt, South Africa: indications from U-Pb and Pb-Pb geochronology

NASA Astrophysics Data System (ADS)

Jaguin, J.; Poujol, M.; Boulvais, P.; Robb, L. J.; Paquette, J. L.

2012-10-01

The 3.09 to 2.97 Ga Murchison Greenstone Belt is an important metallotect in the northern Kaapvaal Craton (South Africa), hosting several precious and base metal deposits. Central to the metallotect is the Antimony Line, striking ENE for over 35 km, which hosts a series of structurally controlled Sb-Au deposits. To the north of the Antimony Line, hosted within felsic volcanic rocks, is the Copper-Zinc Line where a series of small, ca. 2.97 Ga Cu-Zn volcanogenic massive sulfide (VMS)-type deposits occur. New data are provided for the Malati Pump gold mine, located at the eastern end of the Antimony Line. Crystallizations of a granodiorite in the Malati Pump Mine and of the Baderoukwe granodiorite are dated at 2,964 ± 7 and 2,970 ± 7 Ma, respectively (zircon U-Pb), while pyrite associated with gold mineralization yielded a Pb-Pb age of 2,967 ± 48 Ma. Therefore, granodiorite emplacement, sulfide mineral deposition and gold mineralization all happened at ca. 2.97 Ga. It is, thus, suggested that the major styles of orogenic Au-Sb and the Cu-Zn VMS mineralization in the Murchison Greenstone Belt are contemporaneous and that the formation of meso- to epithermal Au-Sb mineralization at fairly shallow levels was accompanied by submarine extrusion of felsic volcanic rocks to form associated Cu-Zn VMS mineralization.

Cooperative cytotoxic activity of Zn and Cu in bovine serum albumin-conjugated ZnS/CuS nano-composites in PC12 cancer cells

NASA Astrophysics Data System (ADS)

Wang, Hua-Jie; Yu, Xue-Hong; Wang, Cai-Feng; Cao, Ying

2013-11-01

Series of self-assembled and mono-dispersed bovine serum albumin (BSA)-conjugated ZnS/CuS nano-composites with different Zn/Cu ratios had been successfully synthesized by a combination method of the biomimetic synthesis and ion-exchange strategy under the gentle conditions. High-resolution transmission electron microscopy observation, Fourier transform infrared spectra and zeta potential analysis demonstrated that BSA-conjugated ZnS/CuS nano-composites with well dispersity had the hierarchical structure and BSA was a key factor to control the morphology and surface electro-negativity of final products. The real-time monitoring by atomic absorption spectroscopy and powder X-ray diffraction revealed that the Zn/Cu ratio of nano-composites could be controlled by adjusting the ion-exchange time. In addition, the metabolic and morphological assays indicated that the metabolic proliferation and spread of rat pheochromocytoma (PC12) cells could be inhibited by nano-composites, with the high anti-cancer activity at a low concentration (4 ppm). What were more important, Zn and Cu in nano-composites exhibited a positive cooperativity at inhibiting cancer cell functions. The microscope observation and biochemical marker analysis clearly revealed that the nano-composites-included lipid peroxidation and disintegration of membrane led to the death of PC12 cells. Summarily, the present study substantiated the potential of BSA-conjugated ZnS/CuS nano-composites as anti-cancer drug.

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits, Central Rhodopes, Bulgaria

NASA Astrophysics Data System (ADS)

Vassileva, Rossitsa D.; Atanassova, Radostina; Kouzmanov, Kalin

2014-08-01

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6-1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe3+. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300-200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.

Outstanding features of Cu-doped ZnS nanoclusters

NASA Astrophysics Data System (ADS)

Tawfik, Wael Z.; Farghali, A. A.; Moneim, Ahmed; Imam, N. G.; El-Dek, S. I.

2018-05-01

ZnS and their Cu-doped nanoclusters (NCs) were synthesized successfully using the wet chemical route with different Cu content. The crystalline structure was investigated using x-ray powder diffraction which assured the single-phase formation in cubic symmetry. High-resolution transmission electron microscope indicated the microstructure of NCs with a size ranging from 2–4 nm. A butterfly hysteresis (M-H) loop was observed at room temperature with large values of coercivity for the Cu content of x = 0.05. Photoluminescence emission spectra were recorded from 500–615 nm for pure and Cu-doped ZnS NCs at a 350 nm excitation wavelength. The sample exhibited green fluorescence bands peaking at 535, 544, 552.5, 558.2, and 560.6 nm, which confirmed the characteristic feature of Zn2+ as luminescent centers in the lattice. The additional yellow and orange emissions are due to defect levels or/and impurity centers. The dielectric constant as well as the conductivity values increased with increasing Cu content.

Phytoextraction of Pb and Cu contaminated soil with maize and microencapsulated EDTA.

PubMed

Xie, Zhiyi; Wu, Longhua; Chen, Nengchang; Liu, Chengshuai; Zheng, Yuji; Xu, Shengguang; Li, Fangbai; Xu, Yanling

2012-09-01

Chelate-assisted phytoextraction using agricultural crops has been widely investigated as a remediation technique for soils contaminated with low mobility potentially toxic elements. Here, we report the use of a controlled-release microencapsulated EDTA (Cap-EDTA) by emulsion solvent evaporation to phytoremediate soil contaminated with Pb and Cu. Incubation experiments were carried out to assess the effect of Cap- and non-microencapsulated EDTA (Ncap-EDTA) on the mobility of soil metals. Results showed EDTA effectively increased the mobility of Pb and Cu in the soil solution and Cap-EDTA application provided lower and more constant water-soluble concentrations of Pb and Cu in comparison with. Phytotoxicity may be alleviated and plant uptake of Pb and Cu may be increased after the incorporation of Cap-EDTA. In addition phytoextraction efficiencies of maize after Cap- and Ncap-EDTA application were tested in a pot experiment. Maize shoot concentrations of Pb and Cu were lower with Cap-EDTA application than with Ncap-EDTA. However, shoot dry weight was significantly higher with Cap-EDTA application. Consequently, the Pb and Cu phytoextraction potential of maize significantly increased with Cap-EDTA application compared with the control and Ncap-EDTA application.

Switching mechanism transition induced by annealing treatment in nonvolatile Cu/ZnO/Cu/ZnO/Pt resistive memory: From carrier trapping/detrapping to electrochemical metallization

NASA Astrophysics Data System (ADS)

Yang, Y. C.; Pan, F.; Zeng, F.; Liu, M.

2009-12-01

ZnO/Cu/ZnO trilayer films sandwiched between Cu and Pt electrodes were prepared for nonvolatile resistive memory applications. These structures show resistance switching under electrical bias both before and after a rapid thermal annealing (RTA) treatment, while it is found that the resistive switching effects in the two cases exhibit distinct characteristics. Compared with the as-fabricated device, the memory cell after RTA demonstrates remarkable device parameter improvements including lower threshold voltages, lower write current, and higher Roff/Ron ratio. A high-voltage forming process is avoided in the annealed device as well. Furthermore, the RTA treatment has triggered a switching mechanism transition from a carrier trapping/detrapping type to an electrochemical-redox-reaction-controlled conductive filament formation/rupture process, as indicated by different features in current-voltage characteristics. Both scanning electron microscopy observations and Auger electron spectroscopy depth profiles reveal that the Cu charge trapping layer in ZnO/Cu/ZnO disperses uniformly into the storage medium after RTA, while x-ray diffraction and x-ray photoelectron spectroscopy analyses demonstrate that the Cu atoms have lost electrons to become Cu2+ ions after dispersion. The above experimental facts indicate that the altered status of Cu in the ZnO/Cu/ZnO trilayer films during RTA treatment should be responsible for the switching mechanism transition. This study is envisioned to open the door for understanding the interrelation between different mechanisms that currently exist in the field of resistive memories.

Facile synthesis of Cu/tetrapod-like ZnO whisker compounds with enhanced photocatalytic properties

NASA Astrophysics Data System (ADS)

Liu, Hong; Liu, Huarong; Fan, Ximei

2017-09-01

Cu/tetrapod-like ZnO whisker (T-ZnOw) compounds were successfully synthesized using N2H4 \\cdot H2O as a reducing agent by a simple reduction method without any insert gas at room temperature. The crystal phase composition and morphology of the as-prepared samples were investigated by XRD, SEM and FESEM tests. The photocatalytic property of the as-prepared samples was detected by the degradation of methyl orange (MO) aqueous solution under UV irradiation. It can be found that Cu nanoparticles (CuNPs) dispersed on the surface of T-ZnOw increased with the increasing of Cu/Zn molar ratios (Cu/Zn MRs), and an octahedral structure of CuNPs was obtained when the sample was prepared with less than and equal to 7.30% Cu/Zn MR, but tended to a spherical or nanorod structure of CuNPs densely arranged on the surface of T-ZnOw, which is prepared by Cu/Zn MRs up to 22.00%. All the compounds exhibited excellent photocatalytic activity in decomposing of MO than T-ZnOw, the photocatalytic property of the samples increased with the increasing of Cu/Zn MRs up to 7.30%, while it decreases when further increasing the Cu/Zn MRs. The Schottky barrier of the Cu/T-ZnOw compound can effectively capture photoinduced electrons from the interface and enhanced the photocatalytic property of T-ZnOw.

Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

PubMed

Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

2013-06-25

Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

First-principles study of defect formation in a photovoltaic semiconductor Cu2ZnGeSe4

NASA Astrophysics Data System (ADS)

Nishihara, Hironori; Maeda, Tsuyoshi; Wada, Takahiro

2018-02-01

The formation energies of neutral Cu, Zn, Ge, and Se vacancies in kesterite-type Cu2ZnGeSe4 were evaluated by first-principles pseudopotential calculations using plane-wave basis functions. The calculations were performed at typical points in Cu-(Zn1/2Ge1/2)-Se and Cu3Se2-ZnSe-GeSe2 pseudoternary phase diagrams for Cu2ZnGeSe4. The results were compared with those for Cu2ZnSnSe4, Cu2ZnGeS4, and Cu2ZnSnS4 calculated using the same version of the CASTEP program code. The results indicate that Cu vacancies are easily formed in Cu2ZnGeSe4 under the Cu-poor condition as in the above compounds and CuInSe2, suggesting that Cu2ZnGeSe4 is also a preferable p-type absorber material for thin-film solar cells. The formation energies of possible antisite defects, such as CuZn and CuGe, and of possible complex defects, such as CuZn+ZnCu, were also calculated and compared within the above materials. The antisite defect of CuZn, which has the smallest formation energy within the possible defects, is concluded to be the most hardly formed in Cu2ZnGeSe4 among the compounds.

Orientation dependence of heterogeneous nucleation at the Cu-Pb solid-liquid interface.

PubMed

Palafox-Hernandez, J Pablo; Laird, Brian B

2016-12-07

In this work, we examine the effect of surface structure on the heterogeneous nucleation of Pb crystals from the melt at a Cu substrate using molecular-dynamics (MD) simulation. In a previous work [Palafox-Hernandez et al., Acta Mater. 59, 3137 (2011)] studying the Cu/Pb solid-liquid interface with MD simulation, we observed that the structure of the Cu(111) and Cu(100) interfaces was significantly different at 625 K, just above the Pb melting temperature (618 K for the model). The Cu(100) interface exhibited significant surface alloying in the crystal plane in contact with the melt. In contrast, no surface alloying was seen at the Cu(111) interface; however, a prefreezing layer of crystalline Pb, 2-3 atomic planes thick and slightly compressed relative to bulk Pb crystal, was observed to form at the interface. We observe that at the Cu(111) interface the prefreezing layer is no longer present at 750 K, but surface alloying in the Cu(100) interface persists. In a series of undercooling MD simulations, heterogeneous nucleation of fcc Pb is observed at the Cu(111) interface within the simulation time (5 ns) at 592 K-a 26 K undercooling. Nucleation and growth at Cu(111) proceeded layerwise with a nearly planar critical nucleus. Quantitative analysis yielded heterogeneous nucleation barriers that are more than two orders of magnitude smaller than the predicted homogeneous nucleation barriers from classical nucleation theory. Nucleation was considerably more difficult on the Cu(100) surface-alloyed substrate. An undercooling of approximately 170 K was necessary to observe nucleation at this interface within the simulation time. From qualitative observation, the critical nucleus showed a contact angle with the Cu(100) surface of over 90°, indicating poor wetting of the Cu(100) surface by the nucleating phase, which according to classical heterogeneous nucleation theory provides an explanation of the large undercooling necessary to nucleate on the Cu(100) surface

Antibacterial activity of trimetal (CuZnFe) oxide nanoparticles.

PubMed

Alzahrani, Khalid E; Niazy, Abdurahman A; Alswieleh, Abdullah M; Wahab, Rizwan; El-Toni, Ahmed M; Alghamdi, Hamdan S

2018-01-01

The increasing resistance of pathogenic bacteria to antibiotics is a challenging worldwide health problem that has led to the search for new and more efficient antibacterial agents. Nanotechnology has proven to be an effective tool for the fight against bacteria. In this paper, we present the synthesis and traits of trimetal (CuZnFe) oxide nanoparticles (NPs) using X-ray diffraction, high-resolution transmission electron microscopy, and energy dispersive x-ray spectroscopy. We evaluated the antibacterial activity of these NPs against gram-negative Escherichia coli and gram-positive Enterococcus faecalis and then compared it to that of their pure single-metal oxide components CuO and ZnO. Our study showed that the antibacterial activity of the trimetal oxide NPs was greater against E . coli than against E . faecalis . Overall, the antimicrobial effect of trimetal NPs is between those of pure ZnO and CuO nanoparticles, which may mean that their cytotoxicity is also between that of pure ZnO and CuO NPs, making them potential antibiotics. However, the cytotoxicity of trimetal NPs to mammalian cells needs to be verified. The combination of three metal oxide NPs (ZnO, CuO, and Fe 2 O 3 ) in one multimetal (CuZnFe) oxide NPs will enhance the therapeutic strategy against a wide range of microbial infections. Bacteria are unlikely to develop resistance against this new NP because bacteria must go through a series of mutations to become resistant to the trimetal oxide NP. Therefore, this NP can combat existing and emerging bacterial infections.

Activities in Cu2S-FeS-PbS melts at 1200 °C

NASA Astrophysics Data System (ADS)

Eriç, H.; Timuçin, M.

1981-09-01

The dew-point method was used to determine the vapor pressures of PbS over liquid sulfides of the system Cu2S-FeS-PbS at 1200 °C. From the PbS activity data, activities of Cu2S and FeS were evaluated both in binary and ternary melts by Gibbs-Duhem calculations. The systems Cu2S-PbS and Cu2S-FeS exhibit negative departures from ideal behavior, while the FeS-PbS melts are ideal solutions at 1200 °C.

Fast photocatalytic degradation of sulforhodamine B using ZnO:Cu nanorods

NASA Astrophysics Data System (ADS)

Raji, R.; Gopchandran, K. G.

2018-02-01

In this work, ZnO:Cu nanorods with tunable Cu content were successfully synthesized via co-precipitation method and investigations were made on the use of these nanorods as photocatalyst by observing the photodegradation of a representative dye pollutant of sulforhodamine B (SRB) under sunlight. The X-ray diffraction analysis and high resolution transmission electron microscopy showed that ZnO:Cu nanorods possess wurtzite phase with preferential growth along (101) plane. The formation of additional defect levels in these nanorods on doping with Cu and its dependence on the concentration of Cu were studied using photoluminescence and X-ray photoelectron spectroscopy. ZnO:Cu nanorods results in faster degradation of dye as compared to the undoped ZnO and is found that Cu doping enhances the photodegradation activity significantly and is highly sensitive to Cu doping level. The fast photocatalytic degradation is attributed to the fact that Cu ions promote the interfacial charge transfer and favors the effective charge separation of photogenerated electrons and holes generated during sunlight irradiation, increasing the rate of production of reactive oxygen species needed for the degradation of the dye. The chemical oxygen demand analysis of the dye solution after sunlight irradiation indicates that rate of mineralization is slower than the decoloration. The possible mechanism for degradation of dye under sunlight irradiation is described with a schematic. Additionally, the photostability of the ZnO:Cu nanorods was also tested through three repetitive cycles. This work suggest that the prepared ZnO:Cu nanorods are suitable for cost-effective water purification.

The effect of Ti-B on stabilization of Cu-Zn-Al martensite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stipcich, M.; Romero, R.

1998-10-05

The application of shape memory effect in devices requires, in many cases, stable and reliable transformation temperatures. However, as a consequence of diffusional processes, in Cu-based shape memory alloys, reverse transformation temperature significantly rises after aging at temperatures above room temperature. This generally unwanted behavior is usually referred to as the stabilization of martensite. Numerous investigations have been carried out on this subject as reviewed by Ahlers and Chandrasekaran et al. Within the Cu-based alloys the Cu-Zn-Al are claimed to be more prone to stabilization than Cu-Al-Ni on aging. It has been proposed that in the Cu-Zn-Al the stabilization ismore » due to the interchange of Cu and Zn atoms assisted by vacancies, changing, consequently, the long range order inherited from the {beta} phase. In the present work, the authors investigate the stabilization behavior of polycrystalline samples of stress induced Cu-Zn-Al and Cu-Zn-Al-B martensite.« less

Preparation of high-permeability NiCuZn ferrite.

PubMed

Hu, Jun; Yan, Mi

2005-06-01

Appropriate addition of CuO/V2O5 and the reduction of the granularity of the raw materials particle decrease the sintering temperature of NiZn ferrite from 1200 degrees C to 930 degrees C. Furthermore, the magnetic properties of the NiZn ferrite prepared at low temperature of 930 degrees C is superior to that of the NiZn ferrite prepared by sintering at high temperature of 1200 degrees C because the microstructure of the NiZn ferrite sintered at 930 degrees C is more uniform and compact than that of the NiZn ferrite sintered at 1200 degrees C. The high permeability of 1700 and relative loss coefficient tandelta/mu(i) of 9.0x10(-6) at 100 kHz was achieved in the (Ni0.17Zn0.63Cu0.20)Fe1.915O4 ferrite.

Partitioning of Dissolved Metals (Fe, Mn, Cu, Cd, Zn, Ni, and Pb) into Soluble and Colloidal Fractions in Continental Shelf and Offshore Waters, Northern California

NASA Astrophysics Data System (ADS)

Fitzsimmons, J. N.; Parker, C.; Sherrell, R. M.

2016-02-01

The physicochemical speciation of trace metals in seawater influences their cycling as essential micronutrients for microorganisms or as tracers of anthropogenic influences on the marine environment. While chemical speciation affects lability, the size of metal complexes influences their ability to be accessed biologically and also influences their fate in the aggregation pathway to marine particles. In this study, we show that multiple trace metals in shelf and open ocean waters off northern California (IRN-BRU cruise, July 2014) have colloidal-sized components. Colloidal fractions were operationally defined using two ultrafiltration methods: a 0.02 µm Anopore membrane and a 10 kDa ( 0.003 µm) cross flow filtration (CFF) system. Together these two methods distinguished small (0.003 - 0.02 µm) and large (0.02 µm - 0.2 µm) colloids. As has been found previously for seawater in other ocean regimes, dissolved Fe had a broad size distribution with 50% soluble (<10 kDa) complexes and both small and large colloidal species. Dissolved Mn had no measurable colloidal component, consistent with its predicted chemical speciation as free Mn(II). Dissolved Cu, which like Fe is thought to be nearly fully organically bound in seawater, was only 25% colloidal, and these colloids were all small. Surprisingly Cd, Ni, and Pb also showed colloidal components (8-20%, 25-40%, and 10-50%) despite their hypothesized low organic speciation. Zn and Pb were nearly completely sorbed onto the Anopore membrane, making CFF the only viable ultrafiltration method for those elements. Zn suffered incomplete recovery ( 50-75%) through the CFF system but showed 30-85% colloidal contribution; thus, verifying a Zn colloidal phase with these methods is challenging. Conclusions will reveal links between the physical and chemical speciation for these metals and what role these metal colloids might have on trace metal exchange between the ocean margin and offshore waters.

Screening and Evaluation of the Bioremediation Potential of Cu/Zn-Resistant, Autochthonous Acinetobacter sp. FQ-44 from Sonchus oleraceus L.

PubMed

Fang, Qing; Fan, Zhengqiu; Xie, Yujing; Wang, Xiangrong; Li, Kun; Liu, Yafeng

2016-01-01

The quest for new, promising and indigenous plant growth-promoting rhizobacteria and a deeper understanding of their relationship with plants are important considerations in the improvement of phytoremediation. This study focuses on the screening of plant beneficial Cu/Zn-resistant strains and assessment of their bioremediation potential (metal solubilization/tolerance/biosorption and effects on growth of Brassica napus seedlings) to identify suitable rhizobacteria and examine their roles in microbes-assisted phytoremediation. Sixty Cu/Zn-resistant rhizobacteria were initially isolated from Sonchus oleraceus grown at a multi-metal-polluted site in Shanghai, China. From these strains, 19 isolates that were all resistant to 300 mg⋅L -1 Cu as well as 300 mg⋅L -1 Zn, and could simultaneously grow on Dworkin-Foster salt minimal medium containing 1-aminocyclopropane-1-carboxylic acid were preliminarily selected. Of those 19 isolates, 10 isolates with superior plant growth-promoting properties (indole-3-acetic acid production, siderophore production, and insoluble phosphate solubilization) were secondly chosen and further evaluated to identify those with the highest bioremediation potential and capacity for bioaugmentation. Strain S44, identified as Acinetobacter sp. FQ-44 based on 16S rDNA sequencing, was specifically chosen as the most favorable strain owing to its strong capabilities to (1) promote the growth of rape seedlings (significantly increased root length, shoot length, and fresh weight by 92.60%, 31.00%, and 41.96%, respectively) under gnotobiotic conditions; (2) tolerate up to 1000 mg⋅L -1 Cu and 800 mg⋅L -1 Zn; (3) mobilize the highest concentrations of water-soluble Cu, Zn, Pb, and Fe (16.99, 0.98, 0.08, and 3.03 mg⋅L -1 , respectively); and (4) adsorb the greatest quantities of Cu and Zn (7.53 and 6.61 mg⋅g -1 dry cell, respectively). Our findings suggest that Acinetobacter sp. FQ-44 could be exploited for bacteria-assisted phytoextraction

Screening and Evaluation of the Bioremediation Potential of Cu/Zn-Resistant, Autochthonous Acinetobacter sp. FQ-44 from Sonchus oleraceus L.

PubMed Central

Fang, Qing; Fan, Zhengqiu; Xie, Yujing; Wang, Xiangrong; Li, Kun; Liu, Yafeng

2016-01-01

The quest for new, promising and indigenous plant growth-promoting rhizobacteria and a deeper understanding of their relationship with plants are important considerations in the improvement of phytoremediation. This study focuses on the screening of plant beneficial Cu/Zn-resistant strains and assessment of their bioremediation potential (metal solubilization/tolerance/biosorption and effects on growth of Brassica napus seedlings) to identify suitable rhizobacteria and examine their roles in microbes-assisted phytoremediation. Sixty Cu/Zn-resistant rhizobacteria were initially isolated from Sonchus oleraceus grown at a multi-metal-polluted site in Shanghai, China. From these strains, 19 isolates that were all resistant to 300 mg⋅L-1 Cu as well as 300 mg⋅L-1 Zn, and could simultaneously grow on Dworkin–Foster salt minimal medium containing 1-aminocyclopropane-1-carboxylic acid were preliminarily selected. Of those 19 isolates, 10 isolates with superior plant growth-promoting properties (indole-3-acetic acid production, siderophore production, and insoluble phosphate solubilization) were secondly chosen and further evaluated to identify those with the highest bioremediation potential and capacity for bioaugmentation. Strain S44, identified as Acinetobacter sp. FQ-44 based on 16S rDNA sequencing, was specifically chosen as the most favorable strain owing to its strong capabilities to (1) promote the growth of rape seedlings (significantly increased root length, shoot length, and fresh weight by 92.60%, 31.00%, and 41.96%, respectively) under gnotobiotic conditions; (2) tolerate up to 1000 mg⋅L-1 Cu and 800 mg⋅L-1 Zn; (3) mobilize the highest concentrations of water-soluble Cu, Zn, Pb, and Fe (16.99, 0.98, 0.08, and 3.03 mg⋅L-1, respectively); and (4) adsorb the greatest quantities of Cu and Zn (7.53 and 6.61 mg⋅g-1 dry cell, respectively). Our findings suggest that Acinetobacter sp. FQ-44 could be exploited for bacteria-assisted phytoextraction. Moreover

(Zn,H)-codoped copper oxide nanoparticles via pulsed laser ablation on Cu-Zn alloy in water

PubMed Central

2012-01-01

Nanosized (5 to 10 nm) amorphous and crystalline nanocondensates, i.e., metallic α-phase of Zn-Cu alloy in face-centered cubic structure and (Zn,H)-codoped cuprite (Cu2O) with high-pressure-favored close-packed sublattice, were formed by pulsed laser ablation on bulk Cu65Zn35 in water and characterized by X-ray/electron diffractions and optical spectroscopy. The as-fabricated hybrid nanocondensates are darkish and showed photoluminescence in the whole visible region. Further dwelling of such nanocondensates in water caused progressive formation of a rice-like assembly of (Zn,H)-codoped tenorite (CuO) nanoparticles with (001), (100), and {111} preferred orientations, (111) tilt boundary, yellowish color, and minimum bandgap narrowing down to ca. 2.7 eV for potential photocatalytic applications. PMID:22647312

Tuning the emission of aqueous Cu:ZnSe quantum dots to yellow light window

NASA Astrophysics Data System (ADS)

Wang, Chunlei; Hu, Zhiyang; Xu, Shuhong; Wang, Yanbin; Zhao, Zengxia; Wang, Zhuyuan; Cui, Yiping

2015-07-01

Synthesis of internally doped Cu:ZnSe QDs in an aqueous solution still suffers from narrow tunable emissions from the blue to green light window. In this work, we extended the emission window of aqueous Cu:ZnSe QDs to the yellow light window. Our results show that high solution pH, multiple injections of Zn precursors, and nucleation doping strategy are three key factors for preparing yellow emitted Cu:ZnSe QDs. All these factors can depress the reactivity of CuSe nuclei and Zn monomers, promoting ZnSe growth outside CuSe nuclei rather than form ZnSe nuclei separately. With increased ZnSe QD size, the conduction band and nearby trap state energy levels shift to higher energy sites, causing Cu:ZnSe QDs to have a much longer emission.

Succulent species differ substantially in their tolerance and phytoextraction potential when grown in the presence of Cd, Cr, Cu, Mn, Ni, Pb, and Zn.

PubMed

Zhang, Chengjun; Sale, Peter W G; Clark, Gary J; Liu, Wuxing; Doronila, Augustine I; Kolev, Spas D; Tang, Caixian

2015-12-01

Plants for the phytoextraction of heavy metals should have the ability to accumulate high concentrations of such metals and exhibit multiple tolerance traits to cope with adverse conditions such as coexistence of multiple heavy metals, high salinity, and drought which are the characteristics of many contaminated soils. This study compared 14 succulent species for their phytoextraction potential of Cd, Cr, Cu, Mn, Ni, Pb, and Zn. There were species variations in metal tolerance and accumulation. Among the 14 succulent species, an Australian native halophyte Carpobrotus rossii exhibited the highest relative growth rate (20.6-26.6 mg plant(-1) day(-1)) and highest tolerance index (78-93%), whilst Sedum "Autumn Joy" had the lowest relative growth rate (8.3-13.6 mg plant(-1) day(-1)), and Crassula multicava showed the lowest tolerance indices (<50%). Carpobrotus rossii and Crassula helmsii showed higher potential for phytoextraction of these heavy metals than other species. These findings suggest that Carpobrotus rossii is a promising candidate for phytoextraction of multiple heavy metals, and the aquatic or semiterrestrial Crassula helmsii is suitable for phytoextraction of Cd and Zn from polluted waters or wetlands.

Comparison of Cu2+ and Zn2+ thermalcatalyst in treating diazo dye

NASA Astrophysics Data System (ADS)

Lau, Y. Y.; Wong, Y. S.; Ong, S. A.; Lutpi, N. A.; Ho, L. N.

2018-05-01

This research demonstrates the comparison between copper (II) sulphate (CuSO4) and zinc oxide (ZnO) as thermalcatalysts in thermolysis process for the treatment of diazo reactive black 5 (RB 5) wastewater. CuSO4 was found to be the most effective thermalcatalyst in comparison to ZnO. The color removal efficiency of RB 5 catalysed by CuSO4 and ZnO were 91.55 % at pH 9.5 and 7.36 % at pH 2, respectively. From the UV-Vis wavelength scan, CuSO4 catalyst is able to cleave the molecular structure bonding more efficiently compared to ZnO. ZnO which only show a slight decay on the main chemical network strands: azo bond, naphthalene and benzene rings whereas CuSO4 catalyst is able to fragment azo bond and naphthalene more effectively. The degradation reactions of CuSO4 and ZnO as thermalcatalysts in thermolysis process were compared.

Biosorption of Cu2+ and Pb2+ using sophora alopecuroides residue

NASA Astrophysics Data System (ADS)

Feng, N.; Fan, W.; Zhu, M.; Zhang, Y.

2016-08-01

Sophora alopecuroides residue (SAP), a kind of traditional Chinese herbal medicine residue, was developed in an alternative biosorbent for the removal Cu2+ and Pb2+ in simulated wastewater. The morphology and surface texture of SAP were characterized by scanning electron microscopy, which showed a loose and porous structure. The biosorption experiments of Cu2+ and Pb2+ onto SAP were investigated by using batch techniques. High biosorption percentage appeared at pH values of 4.5-6.0. The experimental data followed the second-order kinetic model well. Equilibrium fit with the Langmuir isotherm model well. The maximum biosorption capacity of an adsorbent at 25 °C was respectively 60.6 mg/g Cu2+ and 128.1 mg/g Pb2+. The findings of the present study show that SAP is an attractive and effective biosorbent for Cu2+ and Pb2+.

Geochemical contrasts between Late Triassic ore-bearing and barren intrusions in the Weibao Cu-Pb-Zn deposit, East Kunlun Mountains, NW China: constraints from accessory minerals (zircon and apatite)

NASA Astrophysics Data System (ADS)

Zhong, Shihua; Feng, Chengyou; Seltmann, Reimar; Li, Daxin; Dai, Zhihui

2017-12-01

The Weibao copper-lead-zinc skarn deposit is located in the northern East Kunlun terrane, NW China. Igneous intrusions in this deposit consist of barren diorite porphyry (U-Pb zircon age of 232.0 ± 2.0 Ma) and ore-bearing quartz diorite and pyroxene diorite (U-Pb zircon ages of 223.3 ± 1.5 and 224.6 ± 2.9 Ma, respectively). Whole-rock major and trace element and accessory mineral (zircon and apatite) composition from these intrusions are studied to examine the different geochemical characteristics of ore-bearing and barren intrusions. Compared to the barren diorite porphyry, the ore-bearing intrusions have higher Ce4+/Ce3+ ratios of zircon and lower Mn contents of apatite, indicating higher oxidation state. Besides, apatite from the ore-bearing intrusions shows higher Cl contents and lower F/Cl ratios. These characteristics collectively suggest the higher productivity of ore-bearing quartz diorite and pyroxene diorite. When compared with ore-bearing intrusions from global porphyry Cu deposits, those from Cu-Pb-Zn skarn deposits display lower Ce4+/Ce3+ and EuN/EuN* ratios of zircon and lower Cl and higher F/Cl ratios of apatite. We conclude that these differences reflect a general geochemical feature, and that zircon and apatite composition is a sensitive tool to infer economic potential of magmas and the resulting mineralization types in intrusion-related exploration targets.

U-Pb, Re-Os and Ar-Ar dating of the Linghou polymetallic deposit, Southeastern China: Implications for metallogenesis of the Qingzhou-Hangzhou metallogenic belt

NASA Astrophysics Data System (ADS)

Tang, Yanwen; Xie, Yuling; Liu, Liang; Lan, Tingguan; Yang, Jianling; Sebastien, Meffre; Yin, Rongchao; Liang, Songsong; Zhou, Limin

2017-04-01

The Qingzhou-Hangzhou metallogenic belt (QHMB) in Southeastern China has gained increasingly attention in recent years. However, due to the lack of reliable ages on intrusions and associated deposits in this belt, the tectonic setting and metallogenesis of the QHMB have not been well understood. The Linghou polymetallic deposit in northwestern Zhejiang Province is one of the typical deposits of the QHMB. According to the field relationships, this deposit consists of the early Cu-Au-Ag and the late Pb-Zn-Cu mineralization stages. Molybdenite samples with a mineral assemblage of molybdenite-chalcopyrite-pyrite ± quartz are collected from the copper mining tunnel near the Cu-Au-Ag ore bodies. Six molybdenite samples give the Re-Os model ages varying from 160.3 to 164.1 Ma and yield a mean age of 162.2 ± 1.4 Ma for the Cu-Au-Ag mineralization. Hydrothermal muscovite gives a well-defined Ar-Ar isochron age of 160.2 ± 1.1 Ma for the Pb-Zn-Cu mineralization. Three phases of granodioritic porphyry have been distinguished in this deposit, and LA-ICP-MS zircon U-Pb dating shows that they have formed at 158.8 ± 2.4 Ma, 158.3 ± 1.9 Ma and 160.6 ± 2.1 Ma, comparable to the obtained ages of the Cu-Au-Ag and Pb-Zn-Cu mineralization. Therefore, these intrusive rocks have a close temporal and spatial relationship with the Cu-Au-Ag and Pb-Zn-Cu ore bodies. The presences of skarn minerals (e.g., garnet) and vein-type ores, together with the previous fluid inclusion and H-O-C-S-Pb isotopic data, clearly indicate that the Cu-Au-Ag and Pb-Zn-Cu mineralization are genetically related to these granodiorite porphyries. This conclusion excludes the possibility that this deposit is of ;SEDEX; type and formed in a sag basin of continental rifts setting as previously proposed. Instead, it is proposed that the Linghou polymetallic and other similar deposits in the QHMB, such as the 150-160 Ma Yongping porphyry-skarn Cu-Mo, Dongxiang porphyry? Cu, Shuikoushan/Kangjiawang skarn Pb-Zn

Tracing contamination sources in soils with Cu and Zn isotopic ratios.

PubMed

Fekiacova, Z; Cornu, S; Pichat, S

2015-06-01

Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation of high-permeability NiCuZn ferrite*

PubMed Central

Hu, Jun; Yan, Mi

2005-01-01

Appropriate addition of CuO/V2O5 and the reduction of the granularity of the raw materials particle decrease the sintering temperature of NiZn ferrite from 1200 °C to 930 °C. Furthermore, the magnetic properties of the NiZn ferrite prepared at low temperature of 930 °C is superior to that of the NiZn ferrite prepared by sintering at high temperature of 1200 °C because the microstructure of the NiZn ferrite sintered at 930 °C is more uniform and compact than that of the NiZn ferrite sintered at 1200 °C. The high permeability of 1700 and relative loss coefficient tanδ/μi of 9.0×10−6 at 100 kHz was achieved in the (Ni0.17Zn0.63Cu0.20)Fe1.915O4 ferrite. PMID:15909348

The effect of Cu/Zn molar ratio on CO{sub 2} hydrogenation over Cu/ZnO/ZrO{sub 2}/Al{sub 2}O{sub 3} catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaharun, Salina, E-mail: salinashaharun@gmail.com, E-mail: maizats@petronas.com.my; Shaharun, Maizatul S., E-mail: salinashaharun@gmail.com, E-mail: maizats@petronas.com.my; Taha, Mohd F., E-mail: faisalt@petronas.com.my

2014-10-24

Catalytic hydrogenation of carbon dioxide (CO{sub 2}) to methanol is an attractive way to recycle and utilize CO{sub 2}. A series of Cu/ZnO/Al{sub 2}O{sub 3}/ZrO{sub 2} catalysts (CZAZ) containing different molar ratios of Cu/Zn were prepared by the co-precipitation method and investigated in a stirred slurry autoclave system. The catalysts were characterized by temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive analysis (FESEM-EDX), X-ray diffraction (XRD) and N{sub 2} adsorption-desorption. Higher surface area, SA{sub BET} values (42.6–59.9 m{sup 2}/g) are recorded at low (1) and high (5) Cu/Zn ratios with the minimum value of 35.71 m{sup 2}/g found formore » a Cu/Zn of 3. The reducibility of the metal oxides formed after calcination of catalyst samples was also affected due to change in metal-support interaction. At a low reaction temperature of 443 K, total gas pressure of 3.0 MPa and 0.1 g/mL of the CZAZ catalyst, the selectivity to methanol decreased as the Cu/Zn molar ratio increased, and the maximum selectivity of 67.73 was achieved at Cu/Zn molar ratio of 1. With a reaction time of 3h, the best performing catalyst was CZAZ75 with Cu/Zn molar ratio of 5 giving methanol yield of 79.30%.« less

Glomus mosseae enhances root growth and Cu and Pb acquisition of upland rice (Oryza sativa L.) in contaminated soils.

PubMed

Lin, Aijun; Zhang, Xuhong; Yang, Xiaojin

2014-12-01

A pot culture experiment was carried out to investigate the roles of Glomus mosseae in Cu and Pb acquisition by upland rice (Oryza sativa L.) and the interactions between Cu and Pb. The soil was treated with three Cu levels (0, 100 and 200 mg kg(-1)) and three Pb levels (0, 300, and 600 mg kg(-1)). All treatments were designed with (+M) or without (-M) G. mosseae inoculation in a randomized block design. The addition of Cu and Pb significantly decreased root mycorrhizal colonization. Compared with -M, +M significantly increased root biomass in almost all treatments, and also significantly increased shoot biomass in the Pb(0)Cu(200), Pb(300)Cu(0), and all Pb(600) treatments. AM fungi enhanced plant Cu acquisition, but decreased plant Cu concentrations with all Cu plus Pb treatments, except for shoot in the Cu(200)Pb(600) treatment. Irrespective of Cu and Pb levels, +M plants had higher Pb uptakes than -M plants, but had lower root Pb and higher shoot Pb concentrations than those of -M plants. Another interpretation for the higher shoot Pb concentration in +M plants relied on Cu-Pb interactions. The study provided further evidences for the protective effects of AM fungi on upland rice against Cu and Pb contamination, and uncovered the phenomenon that Cu addition could promote Pb uptake and Pb partitioning to shoot. The possible mechanisms by which AM fungi can alleviate the toxicity induced by Cu and Pb are also discussed.

Geochemical behavior of heavy metals in a Zn-Pb-Cu mining area in the State of Mexico (central Mexico).

PubMed

Lizárraga-Mendiola, L; González-Sandoval, M R; Durán-Domínguez, M C; Márquez-Herrera, C

2009-08-01

The geochemical behavior of zinc, lead and copper from sulfidic tailings in a mine site with potential to generate acidic drainage (pyrite (55%) and sphalerite (2%)) is reported in this paper. The mining area is divided in two zones, considering the topographic location of sampling points with respect to the tailings pile: (a) outer zone, out of the probable influence of acid mine drainage (AMD) pollution, and (b) inner zone, probably influenced by AMD pollution. Maximum total ions concentrations (mg/L) measured in superficial waters found were, in the outer zone: As (0.2), Cd (0.9), Fe (19), Mn (39), Pb (5.02), SO4(2-) (4650), Zn (107.67), and in the inner zone are As (0.1), Cd (0.2), Fe (88), Mn (13), Pb (6), SO4(2-) (4,880), Zn (46). The presence of these ions that exceeding the permissible maximum limits for human consume, could be associated to tailings mineralogy and acid leachates generated in tailings pile.

A reconnaissance Rb-Sr, Sm-Nd, U-Pb, and K-Ar study of some host rocks and ore minerals in the West Shasta Cu- Zn district, California ( USA).

USGS Publications Warehouse

Kistler, R.W.; McKee, E.H.; Futa, K.; Peterman, Z.E.; Zartman, R.E.

1985-01-01

The Copley Greenstone, Balaklala Rhyolite, and Mule Mountain stock in the West Shasta Cu-Zn district, California, have Rb-Sr, Sm-Nd, U-Pb, and K-Ar systematics that indicate they are a cogenetic suite of ensimatic island-arc rocks about 400 Ma. Pervasive alteration and mineralization of these rocks, for the most part, was syngenetic and the major component of the mineralizing fluid was Devonian seawater. K-Ar ages of quarz-sericite concentrates from ore horizons and Rb-Sr systematics of a few rock and ore specimens record a later thermal and mineralizing event in the district of about 260 Ma. Contamination of some rocks with pelagic sediments is indicated by the Sm-Nd data. -Authors

Stabilization of lead (Pb) and zinc (Zn) in contaminated rice paddy soil using starfish: A preliminary study.

PubMed

Moon, Deok Hyun; Hwang, Inseong; Koutsospyros, Agamemnon; Cheong, Kyung Hoon; Ok, Yong Sik; Ji, Won Hyun; Park, Jeong-Hun

2018-05-01

Lead (Pb) and zinc (Zn) contaminated rice paddy soil was stabilized using natural (NSF) and calcined starfish (CSF). Contaminated soil was treated with NSF in the range of 0-10 wt% and CSF in the range of 0-5 wt% and cured for 28 days. Toxicity characteristic leaching procedure (TCLP) test was used to evaluate effectiveness of starfish treatment. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) analyses were conducted to investigate the mechanism responsible for effective immobilization of Pb and Zn. Experimental results suggest that NSF and CSF treatments effectively immobilize Pb and Zn in treated rice paddy soil. TCLP levels for Pb and Zn were reduced with increasing NSF and CSF dosage. Comparison of the two treatment methods reveals that CSF treatment is more effective than NSF treatment. Leachability of the two metals is reduced approximately 58% for Pb and 51% for Zn, upon 10 wt% NSF treatment. More pronounced leachability reductions, 93% for Pb and 76% for Zn, are achieved upon treatment with 5 wt% CSF. Sequential extraction results reveal that NSF and CSF treatments of contaminated soil generated decrease in exchangeable/weak acid Pb and Zn soluble fractions, and increase of residual Pb and Zn fractions. Results for the SEM-EDX sample treated with 5 wt% CSF indicate that effective Pb and Zn immobilization is most probably associated with calcium silicate hydrates (CSHs) and calcium aluminum hydrates (CAHs). Copyright © 2018 Elsevier Ltd. All rights reserved.

The concentration of some metals (Pb, Cd, Zn and Cu) and delta aminolevulinic acid dehydratase activity of fruit fly (Drosophila melanogaster) living near lead and zinc smelter ``Trepça'' in Kosova

NASA Astrophysics Data System (ADS)

Elezaj, I. R.; Letaj, K. Rr.; Selimi, Q. I.; Zhushi-Etemi, F.

2003-05-01

The concentration of Pb, Cd, Zn and Cu, δ-aminolevulinic acid dehydratase activity (ALA-D: EC.4.2.1.24) hemoglobin and protein amount have been determined in three different populations of fruit fly (Drosophila melanogaster) caught at two urban sites (Mitrovica town, which is situated close to smelter of “Trepça” don close and Prishtina the capital of Kosova) and in Luki village as uncontaminated area. The results show that in the fruit fly of Mitrovica the concentration of Pb, Cd and Zn was significantly higher (P<0.00l) in comparison with that on the f-Liit fly of Prishtina and Luki. The concentration of Pb of fruit fly from Mitrovica was 3.1 times higher in comparison with that on fruit fly of Prishtina and 4.9 times higher in comparison with uncontaminated group of fruit fly. The ALA-D activity was significantly inhibited in the homogenate of fruit fly from Mitrovica in comparison with Prishtina and Luki localities (P<0.00l). ALA-D activity was also inhibited in the homogenate of Prishtina fruit fly in comparison with Luki group (P<0.00l). The amount of proteins was significantly lower in Mitrovica fruit fly in comparison with that in control and Prishtina group. The hemoglobin value was relatively unchanged.

Heavy metal (As, Cd, Hg, Pb, Cu, Zn, Se) concentrations in muscle and bone of four commercial fish caught in the central Adriatic Sea, Italy.

PubMed

Perugini, Monia; Visciano, Pierina; Manera, Maurizio; Zaccaroni, Annalisa; Olivieri, Vincenzo; Amorena, Michele

2014-04-01

Heavy metal (As, Cd, Cu, Pb, Zn, Hg and Se) concentrations in the muscle and bone of four fish species (Mullus barbatus, Merluccius merluccius, Micromesistius poutassou, and Scomber scombrus) from the central Adriatic Sea were measured and the relationships between fish size (length and weight) and metal concentrations in the tissues were investigated. Samples were analyzed by inductively coupled plasma-atomic emission spectrophotometry with automatic dual viewing. In the muscle, results of linear regression analysis showed that, except for mercury, significant relationships between metal concentrations and fish size were negative. Only mercury levels were positively correlated with Atlantic mackerel size (p < 0.05). No significant variations of heavy metal concentrations were observed in muscles of the examined species, but a significant difference (p < 0.01) was found for As, Cd, Pb, and Se concentrations in bone. All the investigated metals showed higher values in the muscle than in bone, except for lead and zinc. Regarding cadmium, lead, and mercury maximum levels, set for the edible portion by European legislation, several samples exceeded these values, confirming the heavy metal presence in species caught near the Jabuka Pit.

Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

NASA Astrophysics Data System (ADS)

Darma, Yudi; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun; Rusydi, Andrivo

2014-02-01

We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films.

Distribution, origin, and transformation of metal and metalloid pollution in vegetable fields, irrigation water, and aerosols near a Pb-Zn mine.

PubMed

Luo, Liqiang; Chu, Binbin; Liu, Ying; Wang, Xiaofang; Xu, Tao; Bo, Ying

2014-01-01

Pollution of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in vegetable fields was investigated near a Pb-Zn mine that has been exploited for over 50 years without a tailing reservoir. A total of 205 water, soil, and aerosol samples were taken and quantified by combined chemical, spectrometric, and mineral analytical methods. The pollution origins were identified by Pb isotopes and the pathways of transformation and transport of the elements and minerals was studied. The data showed that the vegetable fields were seriously polluted by As, Cd, and Pb. Some concentrations in the samples were beyond the regulatory levels and not suitable for agricultural activities. This study revealed that: (1) particulate matter is a major pollution source and an important carrier of mineral particles and pollutants; (2) the elements from the polluted water and soils were strongly correlated with each other; (3) Pb isotope ratios from the samples show that Pb minerals were the major pollution sources in the nearby vegetable fields, and the aerosols were the main carrier of mining pollution; (4) the alkaline, rich-carbonate, and wet conditions in this area promoted the weathering and transformation of galena into the secondary minerals, anglesite and cerussite, which are significant evidence of such processes; (5) the soil and the aerosols are a recycled secondary pollution source for each other when being re-suspended with wind.Highlights• Mining activities generated heavy metal pollution in fields around a Pb-Zn mine• The elements from water and soils are strongly correlated• Anglesite and cerussite are evidence of galena transformation into secondary minerals• Particulate matter is an important transport carrier of pollution.

Simultaneous increase in strength and ductility by decreasing interface energy between Zn and Al phases in cast Al-Zn-Cu alloy.

PubMed

Han, Seung Zeon; Choi, Eun-Ae; Park, Hyun Woong; Lim, Sung Hwan; Lee, Jehyun; Ahn, Jee Hyuk; Hwang, Nong-Moon; Kim, Kwangho

2017-09-22

Cast-Al alloys that include a high amount of the second element in their matrix have comparatively high strength but low ductility because of the high volume fraction of strengthening phases or undesirable inclusions. Al-Zn alloys that have more than 30 wt% Zn have a tensile strength below 300 MPa, with elongation under 5% in the as-cast state. However, we found that after substitution of 2% Zn by Cu, the tensile strength of as-cast Al-Zn-Cu alloys was 25% higher and ductility was four times higher than for the corresponding Al-35% Zn alloy. Additionally, for the Al-43% Zn alloy with 2% Cu after 1 h solution treatment at 400 °C and water quenching, the tensile strength unexpectedly reached values close to 600 MPa. For the Al-33% Zn alloy with 2% Cu, the tensile strength was 500 MPa with 8% ductility. The unusual trends of the mechanical properties of Al-Zn alloys with Cu addition observed during processing from casting to the subsequent solution treatment were attributed to the precipitation of Zn in the Al matrix. The interface energy between the Zn particles and the Al matrix decreased when using a solution of Cu in Zn.

Pollution and ecological risk assessment of heavy metals in the soil-plant system and the sediment-water column around a former Pb/Zn-mining area in NE Morocco.

PubMed

El Azhari, Abdellah; Rhoujjati, Ali; El Hachimi, Moulay Laârabi; Ambrosi, Jean-Paul

2017-10-01

This study discussed the environmental fate and ecological hazards of heavy metals in the soil-plant system and sediment-water column around the former Pb-Zn mining Zeïda district, in Northeastern Morocco. Spatial distribution, pollution indices, and cluster analysis were applied for assessing Pb, Zn, As, Cu and Cd pollution levels and risks. The geo-accumulation index (I geo ) was determined using two different geochemical backgrounds: i) the commonly used upper crust values, ii) local geochemical background calculated with exploratory data analysis. The soils in the vicinity of the tailings, as well as the sediments downstream of the latter, displayed much higher metal concentrations, I geo, and potential ecology risk coefficient values than other sites, classifying these sites as highly contaminated and severely hazardous. The concentrations of Pb in contaminated sediment samples also exceeded the PEC limits and are expected to cause harmful effects on sediment-dwelling organisms. Based on the comparison with the toxicity limits, the most contaminated plant samples were found around the tailings piles. The metal concentrations in both raw and filtrated water samples were overall below the drinking water standards in samples upstream and downstream of the mining center, indicating that heavy metals levels in the Moulouya River surface waters were not affected by the tailings spill. Cluster analysis suggest that: i) Pb and Zn in sediments were derived from the abandoned tailings and are mainly stored and transported as particle-bound to the bedload, ii) Pb, Zn, and Cu in the soil-plant system were related to the dispersion of tailings materials while As and Cd originated primarily from natural geological background in both the soil-plant and the water-sediment systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Contrasting the material chemistry of Cu 2ZnSnSe 4 and Cu 2ZnSnS (4-x)Se x

DOE PAGES

Aguiar, Jeffery A.; Patel, Maulik; Aoki, Toshihiro; ...

2016-02-02

Earth-abundant sustainable inorganic thin-film solar cells, independent of precious elements, pivot on a marginal material phase space targeting specific compounds. Advanced materials characterization efforts are necessary to expose the roles of microstructure, chemistry, and interfaces. Here, the earth-abundant solar cell device, Cu 2ZnSnS (4-x)Se x, is reported, which shows a high abundance of secondary phases compared to similarly grown Cu 2ZnSnSe 4.

Structural, chemical and optical evaluation of Cu-doped ZnO nanoparticles synthesized by an aqueous solution method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iribarren, A., E-mail: augusto@imre.oc.uh.cu; Hernández-Rodríguez, E.; Maqueira, L.

Highlights: • Cu-doped ZnO nanoparticles obtained by chemical synthesis. • Substitutional or interstitial Cu into ZnO lead specific structural, chemical, and optical changes. • Incorporation efficiency of Cu atoms in ZnO as a function of the Cu concentration in the precursor dissolution. - Abstract: In this work a study of ZnO and Cu-doped ZnO nanoparticles obtained by chemical synthesis in aqueous media was carried out. Structural analysis gave the dominant presence of wurtzite ZnO phase forming a solid solution Zn{sub 1−x}Cu{sub x}O. For high Cu doping CuO phase is also present. For low Cu concentration the lattice shrinks due tomore » Cu atoms substitute Zn atoms. For high Cu concentration the lattice enlarges due to predominance of interstitial Cu. From elemental analysis we determined and analyzed the incorporation efficiency of Cu atoms in Zn{sub 1−x}Cu{sub x}O as a function of the Cu concentration in the precursor dissolution. Combining structural and chemical results we described the Cu/Zn precursor concentrations r{sub w} in which the solid solution of Cu in ZnO is predominant. In the region located at r{sub w} ≈ 0.2–0.3 it is no longer valid. For Cu/Zn precursor concentration r{sub w} > 0.3 interstitial Cu dominates, and some amount of copper oxide appears. As the Cu concentration increases, the effective size of nanoparticles decreases. Photoluminescence (PL) measurements of the Cu-doped ZnO nanoparticles were carried out and analyzed.« less

Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

PubMed Central

Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

2014-01-01

We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material. PMID:24594662

Photovoltaic properties of Cu-doped CH3NH3PbI3 with perovskite structure

NASA Astrophysics Data System (ADS)

Shirahata, Yasuhiro; Oku, Takeo

2017-01-01

Photovoltaic properties of copper (Cu)-doped perovskite (CH3NH3PbCuxI3+x) photovoltaic devices with different Cu content were investigated. The CH3NH3PbCuxI3+x films were polycrystalline with a tetragonal system, and their lattice constants and crystallite size varied with Cu doping. Compared to conversion efficiencies of non-doped CH3NH3PbI3 photovoltaic device, those of CH3NH3PbCuxI3+x photovoltaic devises increased. The improvement of photovoltaic properties was attributed to partial substitution of Cu at the Pb sites.

P-Type Transparent Cu-Alloyed ZnS Deposited at Room Temperature

DOE PAGES

Woods-Robinson, Rachel; Cooper, Jason K.; Xu, Xiaojie; ...

2016-03-16

All transparent conducting materials (TCMs) of technological practicality are n-type; the inferior conductivity of p-type TCMs has limited their adoption. Additionally, many relatively high-performing p-type TCMs require synthesis temperatures > 400 °C. Here, room-temperature pulsed laser deposition of copper-alloyed zinc sulfide (Cu x Zn 1- x S) thin films (0 ≤ x ≤ 0.75) is reported. For 0.09 ≤ x ≤ 0.35, Cu x Zn 1- x S has high p-type conductivity, up to 42 S cm -1 at x = 0.30, with an optical band gap tunable from ≈3.0–3.3 eV and transparency, averaged over the visible, of 50%–71% formore » 200–250 nm thick films. In this range, synchrotron X-ray and electron diffraction reveal a nanocrystalline ZnS structure. Secondary crystalline Cu y S phases are not observed, and at higher Cu concentrations, x > 0.45, films are amorphous and poorly conducting. Furthermore, within the TCM regime, the conductivity is temperature independent, indicating degenerate hole conduction. A decrease in lattice parameter with Cu content suggests that the hole conduction is due to substitutional incorporation of Cu onto Zn sites. This hole-conducting phase is embedded in a less conducting amorphous Cu y S, which dominates at higher Cu concentrations. Finally, the combination of high hole conductivity and optical transparency for the peak conductivity Cu x Zn 1- x S films is among the best reported to date for a room temperature deposited p-type TCM.« less

Changes in heavy metal bioavailability and speciation from a Pb-Zn mining soil amended with biochars from co-pyrolysis of rice straw and swine manure.

PubMed

Meng, Jun; Tao, Mengming; Wang, Lili; Liu, Xingmei; Xu, Jianming

2018-08-15

Biochar has been utilized as a good amendment to immobilize heavy metals in contaminated soils. However, the effectiveness of biochar in metal immobilization depends on biochar properties and metal species. In this study, the biochars produced from co-pyrolysis of rice straw with swine manure at 400°C were investigated to evaluate their effects on bioavailability and chemical speciation of four heavy metals (Cd, Cu, Pb and Zn) in a Pb-Zn contaminated soil through incubation experiment. Results showed that co-pyrolysis process significantly change the yield, ash content, pH, and electrical conductivity (EC) of the blended biochars compared with the single straw/manure biochar. The addition of these biochars significantly increased the soil pH, EC, and dissolved organic carbon (DOC) concentrations. The addition of biochars at a rate of 3% significantly reduced the CaCl 2 -extractable metal concentrations in the order of Pb>Cu>Zn>Cd. The exchangeable heavy metals decreased in all the biochar-amended soils whereas the carbonate-bound metal speciation increased. The increase in soil pH and the decrease in the CaCl 2 extractable metals indicated that these amendments can directly transform the highly availability metal speciation to the stable speciation in soils. In conclusion, biochar derived from co-pyrolysis of rice straw with swine manure at a mass ratio of 3:1 could most effectively immobilize the heavy metals in the soil. Copyright © 2018 Elsevier B.V. All rights reserved.

Pb(core)/ZnO(shell) nanowires obtained by microwave-assisted method

PubMed Central

2011-01-01

In this study, Pb-filled ZnO nanowires [Pb(core)/ZnO(shell)] were synthesized by a simple and novel one-step vapor transport and condensation method by microwave-assisted decomposition of zinc ferrite. The synthesis was performed using a conventional oven at 1000 W and 5 min of treatment. After synthesis, a spongy white cotton-like material was obtained in the condensation zone of the reaction system. HRTEM analysis revealed that product consists of a Pb-(core) with (fcc) cubic structure that preferentially grows in the [111] direction and a hexagonal wurtzite ZnO-(Shell) that grows in the [001] direction. Nanowire length was more than 5 μm and a statistical analysis determined that the shell and core diameters were 21.00 ± 3.00 and 4.00 ± 1.00 nm, respectively. Experimental, structural details, and synthesis mechanism are discussed in this study. PMID:21985637

Chemical fractionation of Cu and Zn in stormwater, roadway dust and stormwater pond sediments

USGS Publications Warehouse

Camponelli, Kimberly M.; Lev, Steven M.; Snodgrass, Joel W.; Landa, Edward R.; Casey, Ryan E.

2010-01-01

This study evaluated the chemical fractionation of Cu and Zn from source to deposition in a stormwater system. Cu and Zn concentrations and chemical fractionation were determined for roadway dust, roadway runoff and pond sediments. Stormwater Cu and Zn concentrations were used to generate cumulative frequency distributions to characterize potential exposure to pond-dwelling organisms. Dissolved stormwater Zn exceeded USEPA acute and chronic water quality criteria in approximately 20% of storm samples and 20% of the storm duration sampled. Dissolved Cu exceeded the previously published chronic criterion in 75% of storm samples and duration and exceeded the acute criterion in 45% of samples and duration. The majority of sediment Cu (92–98%) occurred in the most recalcitrant phase, suggesting low bioavailability; Zn was substantially more available (39–62% recalcitrant). Most sediment concentrations for Cu and Zn exceeded published threshold effect concentrations and Zn often exceeded probable effect concentrations in surface sediments.

The effect of stoichiometry on Cu-Zn ordering kinetics in Cu2ZnSnS4 thin films

NASA Astrophysics Data System (ADS)

Rudisch, Katharina; Davydova, Alexandra; Platzer-Björkman, Charlotte; Scragg, Jonathan

2018-04-01

Cu-Zn disorder in Cu2ZnSnS4 (CZTS) may be responsible for the large open circuit voltage deficit in CZTS based solar cells. In this study, it was investigated how composition-dependent defect complexes influence the order-disorder transition. A combinatorial CZTS thin film sample was produced with a cation composition gradient across the sample area. The graded sample was exposed to various temperature treatments and the degree of order was analyzed with resonant Raman spectroscopy for various compositions ranging from E- and A-type to B-, F-, and C-type CZTS. We observe that the composition has no influence on the critical temperature of the order-disorder transition, but strongly affects the activation energy. Reduced activation energy is achieved with compositions with Cu/Sn > 2 or Cu/Sn < 1.8 suggesting an acceleration of the cation ordering in the presence of vacancies or interstitials. This is rationalized with reference to the effect of point defects on exchange mechanisms. The implications for reducing disorder in CZTS thin films are discussed in light of the new findings.

[Remediation of Cu-Pb-contaminated loess soil by leaching with chelating agent and biosurfactant].

PubMed

Liu, Xia; Wang, Jian-Tao; Zhang, Meng; Wang, Li; Yang, Ya-Ti

2013-04-01

Because of its strong chelation, solubilization characteristics, the chelating agents and biosurfactant are widely used in remediation of heavy metals and organic contaminated soils. Ethylenediamine tetraacetic acid (EDTA), citric acid (CIT) and dirhamnolipid (RL2) were selected as the eluent. Batch experiments and column experiments were conducted to investigate the leaching effect of the three kinds of eluent, as well as the mixture of biosurfactant and chelating agent for Cu, Pb contaminated loess soil. The results showed that the leaching efficiencies of different eluent on Cu, Pb contaminated loess soil followed the sequence of EDTA > CIT > RL2. At an eluent concentration of 0.02 mol x L(-1), the Cu leaching efficiency was 62.74% (EDTA), 52.28% (CIT) and 15.35% (RL2), respectively; the Pb leaching efficiency was 96.10% (EDTA), 23.08% (CIT) and 14.42% (RL2), respectively. When the concentration of RL2 was 100 CMC, it had synergistic effects on the other two kinds of chelating agent in Cu leaching, and when the concentration of RL2 was 200 CMC, it had antagonism effects. The effect of RL2 on EDTA in Pb leaching was similar to that in Cu leaching. Pb leaching by CIT was inhibited in the presence of RL2. EDTA and CIT could effectively remove Cu and Pb in exchangeable states, adsorption states, carbonate salts and organic bound forms; RL2 could effectively remove Cu and Pb in exchangeable and adsorbed states.

Non-blinking (Zn)CuInS/ZnS Quantum Dots Prepared by In Situ Interfacial Alloying Approach

PubMed Central

Zhang, Aidi; Dong, Chaoqing; Li, Liang; Yin, Jinjin; Liu, Heng; Huang, Xiangyi; Ren, Jicun

2015-01-01

Semiconductor quantum dots (QDs) are very important optical nanomaterials with a wide range of potential applications. However, blinking behavior of single QD is an intrinsic drawback for some biological and photoelectric applications based on single-particle emission. Herein we present a rational strategy for fabrication of non-blinking (Zn)CuInS/ZnS QDs in organic phase through in situ interfacial alloying approach. This new strategy includes three steps: synthesis of CuInS QDs, eliminating the interior traps of QDs by forming graded (Zn)CuInS alloyed QDs, modifying the surface traps of QDs by introducing ZnS shells onto (Zn)CuInS QDs using alkylthiols as sulfur source and surface ligands. The suppressed blinking mechanism was mainly attributed to modifying QDs traps from interior to exterior via a step-by-step modification. Non-blinking QDs show high quantum yield, symmetric emission spectra and excellent crystallinity, and will enable applications from biology to optoelectronics that were previously hindered by blinking behavior of traditional QDs. PMID:26458511

Isolation and characterization of Cu/Zn-superoxide dismutase in Fasciola gigantica.

PubMed

Lalrinkima, H; Raina, O K; Chandra, Dinesh; Jacob, Siju Susan; Bauri, R K; Chandra, Subhash; Yadav, H S; Singh, M N; Rialch, A; Varghese, A; Banerjee, P S; Kaur, Navneet; Sharma, Arvind

2015-01-01

A full-length complementary DNA (cDNA) encoding Cu/Zn-superoxide dismutase was isolated from Fasciola gigantica that on nucleotide sequencing showed a close homology (98.9%) with Cu/Zn-superoxide dismutase (SOD) of the temperate liver fluke, F. hepatica. Expression of the gene was found in all the three developmental stages of the parasite viz. adult, newly excysted juvenile and metacercaria at transcriptional level by reverse transcription-polymerase chain reaction (RT-PCR) and at the protein level by Western blotting. F. gigantica Cu/Zn-SOD cDNA was cloned and expressed in Escherichia coli. Enzyme activity of the recombinant protein was determined by nitroblue tetrazolium (NBT)-polyacrylamide gel electrophoresis (PAGE) and this activity was inactivated by hydrogen peroxide but not by sodium azide, indicating that the recombinant protein is Cu/Zn-SOD. The enzyme activity was relatively stable at a broad pH range of pH 4.0-10.0. Native Cu/Zn-superoxide dismutase protein was detected in the somatic extract and excretory-secretory products of the adult F. gigantica by Western blotting. NBT-PAGE showed a single Cu/Zn-SOD present in the somatic extract while three SODs are released ex vivo by the adult parasite. The recombinant superoxide dismutase did not react with the serum from buffaloes infected with F. gigantica. The role of this enzyme in defense by the parasite against the host reactive oxygen species is discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

NASA Astrophysics Data System (ADS)

Wang, Kejia; Shin, Byungha; Reuter, Kathleen B.; Todorov, Teodor; Mitzi, David B.; Guha, Supratik

2011-01-01

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu-Sn-S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

Pollution of soils (Pb, Cd, Cr, Zn, Cu, Ni) along the ring road of Wrocław (Poland)

NASA Astrophysics Data System (ADS)

Hołtra, Anna; Zamorska-Wojdyła, Dorota

2017-11-01

The concentrations of metallic pollution in soils and plants along the ring road of Wrocław, Poland, have been determined. Environmental samples were collected from the surface layer of the profile within 2-3 m from the edge of the road. The analysis of metals (Pb, Cd, Cr, Zn, Cu and Ni) has been carried out through FAAS and GFAAS methods. The mineralizates of soils and plants were prepared in HNO3, 65% supra pure, using the Microwave Digestion System. The pH and conductivity of the soil solutions were measured to evaluate their active and exchangeable acidity and the salinity of the soils. The index of the enrichment of soils in metals (Wn) and the bioaccumulation coefficient (WB) have been determined. Also, histograms of the frequency of the occurrence of metals in the environmental samples and the Pearson's correlation coefficients were presented. The results of metal concentrations in soils were compared to the geochemical background in uncontaminated soils of Poland. The assessment of the results in the soils was also made relative to the standard, according to the Polish Ministry of Environment Regulation from September 1st, 2016. During the assessment of the bioaccumulation coefficients of metals in plants a reference was made to the content of undesirable substances in feed in agreement with the Polish Ministry of Agriculture and Rural Development Regulation from January 23rd, 2007.

Evidence for microbial activity in the formation of carbonate-hosted Zn-Pb deposits

NASA Astrophysics Data System (ADS)

Kucha, H.; Raith, J.

2009-04-01

*Kucha H **Raith J *University of Mining and Metallurgy, Faculty of Geology, Geophysics and Environmental Protection, Mickiewicza 30, PL-30-059 Krakow, Poland. ** University of Leoben, Department of Applied Geosciences and Geophysics, A-8700 Leoben, Peter Tunner Str. 5, Austria Evidence for microbial activity in the formation of carbonate-hosted Zn-Pb deposits To date evaluation of bacterial processes in the formation of carbonate-hosted Zn-Pb deposits is largely based on sulphur isotope evidence. However, during a past few years, textural criteria, have been established, which support the bacterial origin of many of these deposits. This has received a strong support from micro-, and nano-textures of naturally growing bacterial films in a flooded tunnel within carbonates that host the Piquette Zn-Pb deposit (Druschel et al., 2002). Bacterial textures, micro- and nano textures found in carbonate-hosted Zn-Pb deposits are: i)wavy bacterial films up to a few mm thick to up to a few cm long composed of peloids, ii)semimassive agglomeration of peloids in the carbonate matrix, and iii)solitary peloids dispersed in the carbonate matrix. Peloids are usually composed of a distinct 50-90um core most often made up of Zn-bearing calcite surrounded by 30-60um thick dentate rim composed of ZnS. Etching of Zn-carbonate cores reveals 1 - 2um ZnS filaments, and numerous 15 to 90nm large ZnS nano-spheres (Kucha et al., 2005). In massive ore composite Zn-calcite - sphalerite peloids are entirely replaced by zinc sulphide, and form peloids ghosts within banded sulphide layers. Bacterially derived micro- and nano-textures have been observed in the following carbonate-hosted Zn-Pb deposits: 1)Irish-type Zn-Pb deposits. In the Navan deposit the basic sulphur is isotopically light bacteriogenic S (Fallick at al., 2001). This is corroborated by semimassive agglomerations of composite peloids (Zn-calcite-ZnS corona or ZnS core-melnikovite corona). Etching of Zn-calcite core reveals globular

Critical elements in sediment-hosted deposits (clastic-dominated Zn-Pb-Ag, Mississippi Valley-type Zn-Pb, sedimentary rock-hosted Stratiform Cu, and carbonate-hosted Polymetallic Deposits): A review: Chapter 12

USGS Publications Warehouse

Marsh, Erin; Hitzman, Murray W.; Leach, David L.

2016-01-01

Some sediment-hosted base metal deposits, specifically the clastic-dominated (CD) Zn-Pb deposits, carbonate-hosted Mississippi Valley-type (MVT) deposits, sedimentary-rock hosted stratiform copper deposits, and carbonate-hosted polymetallic (“Kipushi type”) deposits, are or have been important sources of critical elements including Co, Ga, Ge, and Re. The generally poor data concerning trace element concentrations in these types of sediment-hosted ores suggest that there may be economically important concentrations of critical elements yet to be recognized.

Effects of CuZnAl Particles on Properties and Microstructure of Sn-58Bi Solder

PubMed Central

Yang, Fan; Zhang, Liang; Liu, Zhi-quan; Zhong, Su Juan; Ma, Jia; Bao, Li

2017-01-01

With the purpose of improving the properties of the Sn-58Bi lead-free solder, micro-CuZnAl particles ranging from 0 to 0.4 wt % were added into the low temperature eutectic Sn-58Bi lead-free solder. After the experimental testing of micro-CuZnAl particles on the properties and microstructure of the Sn-58Bi solders, it was found that the wettability of the Sn-58Bi solders was obviously improved with addition of CuZnAl particles. When the addition of CuZnAl particles was 0.2 wt %, the wettability of the Sn-58Bi solder performed best. At the same time, excessive addition of CuZnAl particles led to poor wettability. However, the results showed that CuZnAl particles changed the melting point of the Sn-58Bi solder slightly. The microstructure of the Sn-58Bi solder was refined by adding CuZnAl particles. When the content of CuZnAl addition was between 0.1 and 0.2 wt %, the refinement was great. In addition, the interfacial IMC layer between new composite solder and Cu substrate was thinner than that between the Sn-58Bi solder and Cu substrate. PMID:28772917

Hybrid polymer/ZnO solar cells sensitized by PbS quantum dots

PubMed Central

2012-01-01

Poly[2-methoxy-5-(2-ethylhexyloxy-p-phenylenevinylene)]/ZnO nanorod hybrid solar cells consisting of PbS quantum dots [QDs] prepared by a chemical bath deposition method were fabricated. An optimum coating of the QDs on the ZnO nanorods could strongly improve the performance of the solar cells. A maximum power conversion efficiency of 0.42% was achieved for the PbS QDs' sensitive solar cell coated by 4 cycles, which was increased almost five times compared with the solar cell without using PbS QDs. The improved efficiency is attributed to the cascade structure formed by the PbS QD coating, which results in enhanced open-circuit voltage and exciton dissociation efficiency. PMID:22313746

Kinetic sorption modelling of Cu, Ni, Zn, Pb and Cr ions to pine bark and blast furnace slag by using batch experiments.

PubMed

Nehrenheim, E; Gustafsson, J P

2008-04-01

Storm water and landfill leachate can both contain significant amounts of toxic metals such as Zn, Cu, Pb, Cr and Ni. Pine bark and blast furnace slag are both residual waste products that have shown a large potential for metal removal from contaminated water. There are however many variables that must be optimized in order to achieve efficient metal retention. One of these variables is the time of which the solution is in contact with each unit of filter material. Metal sorption was studied in two laboratory experiments to improve the knowledge of the effects of contact time. The results showed that pine bark was generally more efficient than blast furnace slag when the metal concentrations were relatively small, whereas blast furnace slag sorbed most metals to a larger extent at increased metal loads. In addition, sorption to blast furnace slag was found to be faster than metal binding to pine bark. A pseudo-second-order kinetic model was able to describe the data well within 1000 s of reaction time.

Transparent Cu4O3/ZnO heterojunction photoelectric devices

NASA Astrophysics Data System (ADS)

Kim, Hong-Sik; Yadav, Pankaj; Patel, Malkeshkumar; Kim, Joondong; Pandey, Kavita; Lim, Donggun; Jeong, Chaehwan

2017-12-01

The present article reports the development of flexible, self-biased, broadband, high speed and transparent heterojunction photodiode, which is essentially important for the next generation electronic devices. We grow semitransparent p-type Cu4O3 using the reactive sputtering method at room temperature. The structural and optical properties of the Cu4O3 film were investigated by using the X-ray diffraction and UV-visible spectroscopy, respectively. The p-Cu4O3/n-ZnO heterojunction diode under dark condition yields rectification behavior with an extremely low saturation current value of 1.8 × 10-10 A and a zero bias photocurrent under illumination condition. The transparent p-Cu4O3/n-ZnO heterojunction photodetector can be operated without an external bias, due to the light-induced voltage production. The metal oxide heterojunction based on Cu4O3/ZnO would provide a route for the transparent and flexible photoelectric devices, including photodetectors and photovoltaics.

Self-Assembled Formation of Well-Aligned Cu-Te Nano-Rods on Heavily Cu-Doped ZnTe Thin Films

NASA Astrophysics Data System (ADS)

Liang, Jing; Cheng, Man Kit; Lai, Ying Hoi; Wei, Guanglu; Yang, Sean Derman; Wang, Gan; Ho, Sut Kam; Tam, Kam Weng; Sou, Iam Keong

2016-11-01

Cu doping of ZnTe, which is an important semiconductor for various optoelectronic applications, has been successfully achieved previously by several techniques. However, besides its electrical transport characteristics, other physical and chemical properties of heavily Cu-doped ZnTe have not been reported. We found an interesting self-assembled formation of crystalline well-aligned Cu-Te nano-rods near the surface of heavily Cu-doped ZnTe thin films grown via the molecular beam epitaxy technique. A phenomenological growth model is presented based on the observed crystallographic morphology and measured chemical composition of the nano-rods using various imaging and chemical analysis techniques. When substitutional doping reaches its limit, the extra Cu atoms favor an up-migration toward the surface, leading to a one-dimensional surface modulation and formation of Cu-Te nano-rods, which explain unusual observations on the reflection high energy electron diffraction patterns and apparent resistivity of these thin films. This study provides an insight into some unexpected chemical reactions involved in the heavily Cu-doped ZnTe thin films, which may be applied to other material systems that contain a dopant having strong reactivity with the host matrix.

μSR investigation of a new diluted magnetic semiconductor Li(Zn,Mn,Cu)As with Mn and Cu codoping at the same Zn sites

NASA Astrophysics Data System (ADS)

Guo, S. L.; Zhao, Y.; Man, H. Y.; Ding, C.; Gong, X.; Zhi, G. X.; Fu, L. C.; Gu, Y. L.; Frandsen, B. A.; Liu, L.; Cheung, S. C.; Munsie, T. J.; Wilson, M. N.; Cai, Y. P.; Luke, G. M.; Uemura, Y. J.; Ning, F. L.

2016-09-01

We report the successful synthesis and characterization of a new type I-II-V bulk form diluted magnetic semiconductor (DMS) Li(Zn,Mn,Cu)As, in which charge and spin doping are decoupled via (Cu,Zn) and (Mn,Zn) substitution at the same Zn sites. Ferromagnetic transition temperature up to  ˜33 K has been observed with a coercive field  ˜40 Oe for the 12.5% doping level. μSR measurements confirmed that the magnetic volume fraction reaches nearly 100% at 2 K, and the mechanism responsible for the ferromagnetic interaction in this system is the same as other bulk form DMSs.

Nucleoside-2',3'/3',5'-bis(thio)phosphate antioxidants are also capable of disassembly of amyloid beta42-Zn(ii)/Cu(ii) aggregates via Zn(ii)/Cu(ii)-chelation.

PubMed

Hevroni, Bosmat Levi; Major, Dan Thomas; Dixit, Mudit; Mhashal, Anil Ranu; Das, Susanta; Fischer, Bilha

2016-05-18

Currently, there is an urgent need for biocompatible metal-ion chelators capable of antioxidant activity and disassembly of amyloid beta (Aβ)-aggregates as potential therapeutics for Alzheimer's disease (AD). We recently demonstrated the promising antioxidant activity of adenine/guanine 2',3' or 3',5'-bis(thio)phosphate analogues, 2'-dA/G3'5'PO/S and A2'3'PO/S, and their affinity to Zn(ii)-ions. These findings encouraged us to evaluate them as agents for the dissolution of Aβ42-Zn(ii)/Cu(ii) aggregates. Specifically, we explored their ability to bind Cu(ii)/Zn(ii)-ions, the geometry and stoichiometry of these complexes, Cu(ii)/Zn(ii)-binding-sites and binding mode, and the ability of these analogues to dissolve Aβ42-Zn(ii)/Cu(ii) aggregates, as well as their effect on the secondary structure of those aggregates. Finally, we identified the most promising agents for dissolution of Aβ42-Zn(ii)/Cu(ii) aggregates. Specifically, we observed the formation of a 1 : 1 complex between 2'-dG3'5'PO and Cu(ii), involving O4 ligands. Zn(ii) was coordinated by both thiophosphate groups of 2'-dA3'5'PS and A2'3'PS involving O2S2 ligands in a 1 : 1 stoichiometry. A2'3'PS dissolves Aβ42-Zn(ii) and Aβ42-Cu(ii) aggregates as effectively as, and 2.5-fold more effectively than EDTA, respectively. Furthermore, 2'-dG3'5'PS and A2'3'PS reverted the Aβ42-M(ii) structure, back to that of the free Aβ42. Finally, cryo-TEM and TEM images confirmed the disassembly of Aβ42 and Aβ42-M(ii) aggregates by A2'3'PS. Hence, 2'-dG3'5'PS and A2'3'PS may serve as promising scaffolds for new AD therapeutics, acting as both effective antioxidants and agents for solubilization of Aβ42-Cu(ii)/Zn(ii) aggregates.

Investigation of transport properties of ZnO/PbS heterojunction solar cells

NASA Astrophysics Data System (ADS)

Cheng, Yang; Whitaker, Michael D. C.; Whiteside, Vincent R.; Bumm, Lloyd A.; Sellers, Ian R.

Lead sulfide (PbS) and lead selenide (PbSe) colloidal quantum dots (CQDs) are considered as a potential candidate material for solar cell applications due to their large band gap tunability range (0.5 to 1.7 eV) and cost-effective solution based processing. A series of Glass/ITO/ZnO/PbS/MoO3/Au heterojunction solar cells were processed and analyzed. A stable (reproducible) 2% conversion efficiency under 1-sun is achieved based on the result of J - V measurements. Absorbance and external quantum efficiency (EQE) measurements clearly show photo-generated carrier extraction from PbS active layers in the solar cell. However, a non-ideal J - V behavior is observed in current-voltage measurements. This behavior may be attributed to a high density of trap states at the QD surface or defect states at the PbS/ZnO or ITO/ZnO interfaces. C-V and Impedance spectroscopy measurements are used to study this unusual behavior. These techniques could also help probe the transport properties and limitation of these heterojunction solar cells. This research is funded through NASA EPSCoR program Award # NNX13AN101A.

Health risks of heavy metal exposure through vegetable consumption near a large-scale Pb/Zn smelter in central China.

PubMed

Li, Xinyu; Li, Zhonggen; Lin, Che-Jen; Bi, Xiangyang; Liu, Jinling; Feng, Xinbin; Zhang, Hua; Chen, Ji; Wu, Tingting

2018-06-04

Smelting of nonferrous metals is an important source of heavy metals in surface soil. The crops/vegetables grown on contaminated soil potentially impose adverse effects on human health. In this study, the contamination level of five heavy metals (Hg, Pb, Zn, Cd and Cu) in ten types of vegetables grown nearby a large scale Pb/Zn smelter in Hunan Province, China and the health risk associated with their consumption are assessed. Based on the data obtained from 52 samples, we find that Pb and Cd contributed to the greatest health risk and leafy vegetables tend to be more contaminated than non-leafy vegetables. Within 4 km radius of the smelter, over 75% of vegetable samples exceeded the national food standard for Pb; over 47% exceeded the Cd standard; and 7% exceeded the Hg standard. Heavy metal concentrations in vegetables measured within the 4 km radius are on average three times more elevated compared to those found at the control area 15 km away. Heavy metals in vegetables have dual sources of root absorption from soil and leaf adsorption from atmosphere. Health risk in terms of the hazard index (HI) at contaminated areas are 3.66 and 3.14 for adults and children, respectively, suggesting adverse health effects would occur. HI for both groups are mainly contributed by Pb (48%) and Cd (40%). Fortunately, vegetable samples collected at the control area are considered safe to consume. Copyright © 2018 Elsevier Inc. All rights reserved.

Field evaluation of the effectiveness of three industrial by-products as organic amendments for phytostabilization of a Pb/Zn mine tailings.

PubMed

Yang, Shengxiang; Cao, Jianbing; Li, Fengmei; Peng, Xizhu; Peng, Qingjing; Yang, Zhihui; Chai, Liyuan

2016-01-01

Although the potential of industrial by-products as organic amendments for phytostabilization has long been recognized, most of the previous studies addressing this issue have been laboratory-based. In this study, a field trial was conducted to evaluate the effectiveness of three industrial by-products [sweet sorghum vinasse (SSV), medicinal herb residues (MHR) and spent mushroom compost (SMC)] as organic amendments for phytostabilization of abandoned Pb/Zn mine tailings. Our results showed the following: (i) when compared to the control tailings, the mean concentrations of diethylene-triamine-pentaacetic acid (DTPA)-extractable Cd, Cu, Pb and Zn in SSV, MHR and SMC treatments decreased by 20.8-28.0%, 41.6-49.1%, 17.7-22.7% and 9.5-14.7%, respectively; (ii) the mean values of organic C, ammonium-N and available P in SSV, MHR and SMC treatments increased by 1.7-2.8, 10.8-14.9 and 3.9-5.1 times as compared with the mine tailings; and (iii) the addition of SSV, MHR and SMC significantly enhanced soil respiration and microbial biomass being 1.5-1.8 and 1.3-1.6 fold higher than those in the control tailings. There were no significant differences in soil biochemical properties among the plots amended with these by-products, suggesting that they were almost equally effective in improving the biochemical conditions of the tailings. In addition, the application of these amendments promoted seed germination, seedling growth, and consequently increased the vegetation cover and its biomass. Moreover, concentrations of Cd, Cu, Pb and Zn in above-ground parts of the plants were below the toxicity limit levels for animals. The results obtained in this field study confirmed that the three organic-rich industrial by-products could be used as amendments for phytostabilization of some types of mine tailings.

Stabilization of As-, Pb-, and Cu-contaminated soil using calcined oyster shells and steel slag.

PubMed

Moon, Deok Hyun; Wazne, Mahmoud; Cheong, Kyung Hoon; Chang, Yoon-Young; Baek, Kitae; Ok, Yong Sik; Park, Jeong-Hun

2015-07-01

In this study, As-, Pb-, and Cu-contaminated soil was stabilized using calcined oyster shells (COS) and steel slag (SS). The As-contaminated soil was obtained from a timber mill site where chromate copper arsenate (CCA) was used as a preservative. On the other hand, Pb- and Cu-contaminated soil was obtained from a firing range. These two soils were thoroughly mixed to represent As-, Pb-, and Cu-contaminated soil. Calcined oyster shells were obtained by treating waste oyster shells at a high temperature using the calcination process. The effectiveness of stabilization was evaluated by 1-N HCl extraction for As and 0.1-N HCl extraction for Pb and Cu. The treatment results showed that As, Pb, and Cu leachability were significantly reduced upon the combination treatment of COS and SS. The sole treatment of SS (10 wt%) did not show effective stabilization. However, the combination treatment of COS and SS showed a significant reduction in As, Pb, and Cu leachability. The best stabilization results were obtained from the combination treatment of 15 wt% COS and 10 wt% SS. The SEM-EDX results suggested that the effective stabilization of As was most probably achieved by the formation of Ca-As and Fe-As precipitates. In the case of Pb and Cu, stabilization was most probably associated with the formation of pozzolanic reaction products such as CSHs and CAHs.

Microstructures and Mechanical Properties of Cu and Cu-Zn Alloys

NASA Astrophysics Data System (ADS)

Ma, Xiaolong

Strength and ductility are two crucial mechanical properties of structural materials, which, unfortunately, are often mutually exclusive based on the conventional design of microstructures and their deformation physics. This is also true in most nanostructured (NS) metals and alloys although they exhibit record-high strength. However, the disappointingly inadequate ductility becomes the major roadblock to their practical utilities due to the threat of catastrophic failure in load-bearing applications. Therefore, simultaneous improvement of strength and ductility or a well-defined trade-off between these two properties, i.e. increasing either of them without significant loss of the other, in NS materials has garnered extensive efforts from the research community. A few strategies have been explored to handle this long-standing challenge with promise. In this dissertation work, two of those strategies, deformation twins and laminate/gradient structures are specified with particular interests in NS Cu and Cu-Zn alloys. The author believes the observation and the revealed underlying mechanism are fundamental and therefore shed lights on their universal application to other metallic material systems. Deformation twins have been frequently observed in ultra-fined grained (UFG) and NS face-centered cubic (FCC) metals and alloys, which is closely related to the better strengthening and strain hardening in mechanical performance. Previous findings even show that there exist an optimum grain size range within nano scale, where the deformation twins are of most frequency, i.e. most stable in pure FCC metals. However, such grain-size dependent twinning phenomenon is still unclear in FCC alloys. We report, for the first time in systematic experiments, the observed optimum grain sizes for deformation twins in NS Cu-Zn alloys slightly increase with increasing Zn content. Our results indicate that alloying changes the relationship between the stacking-fault and twin-fault energy

Characteristic of total suspended particulate (TSP) containing Pb and Zn at solid waste landfill

NASA Astrophysics Data System (ADS)

Budihardjo, M. A.; Noveandra, K.; Samadikun, B. P.

2018-05-01

Activities conducted at municipal solid waste landfills (MSWLs) potentially cause air pollution. Heavy vehicles in MSWLs release various pollutants that can have negative impacts for humans. One noticeable pollutant at MSWLs is airborne total suspended particulate (TSP) which may contain heavy metals such as Pb and Zn and can cause disease when inhaled by humans. In this study, TSP from a landfill in Semarang, Indonesia was collected and characterized to quantify the concentration of Pb and Zn. Meteorological factors (i.e. temperature, humidity and wind velocity) and landfill activities were considered as factors affecting pollutant concentrations. TSP was sampled using dust samplers while the concentrations of heavy metals in TSP were analyzed using an Atomic Absorption Spectrophotometer (AAS). Pb concentration ranged from 0.84 to 1.78 µg/m3 while Zn concentration was from 7.87 to 8.76 µg/m3. The levels of Pb were below the threshold specified by the Indonesian Government. Meanwhile, the threshold for Zn has not yet been determined.

Functional Performances of CuZnAl Shape Memory Alloy Open-Cell Foams

NASA Astrophysics Data System (ADS)

Biffi, C. A.; Casati, R.; Bassani, P.; Tuissi, A.

2018-01-01

Shape memory alloys (SMAs) with cellular structure offer a unique mixture of thermo-physical-mechanical properties. These characteristics can be tuned by changing the pore size and make the shape memory metallic foams very attractive for developing new devices for structural and functional applications. In this work, CuZnAl SMA foams were produced through the liquid infiltration of space holder method. In comparison, a conventional CuZn brass alloy was foamed trough the same method. Functional performances were studied on both bulk and foamed SMA specimens. Calorimetric response shows similar martensitic transformation (MT) below 0 °C. Compressive response of CuZnAl revealed that mechanical behavior is strongly affected by sample morphology and that damping capacity of metallic foam is increased above the MT temperatures. The shape memory effect was detected in the CuZnAl foams. The conventional brass shows a compressive response similar to that of the martensitic CuZnAl, in which plastic deformation accumulation occurs up to the cellular structure densification after few thermal cycles.

Ice-core based assessment of historical anthropogenic heavy metal (Cd, Cu, Sb, Zn) emissions in the Soviet Union.

PubMed

Eichler, Anja; Tobler, Leonhard; Eyrikh, Stella; Malygina, Natalia; Papina, Tatyana; Schwikowski, Margit

2014-01-01

The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935-1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control.

Facile synthesis and photocatalytic activity of bi-phase dispersible Cu-ZnO hybrid nanoparticles

NASA Astrophysics Data System (ADS)

Liu, Xiao; Liu, HongLing; Zhang, WenXing; Li, XueMei; Fang, Ning; Wang, XianHong; Wu, JunHua

2015-04-01

Bi-phase dispersible Cu-ZnO hybrid nanoparticles were synthesized by one-pot non-aqueous nanoemulsion with the use of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) show high crystallinity of the Cu-ZnO hybrid nanoparticles and an average particle size of ~19.4 nm. The ultraviolet-visible light absorbance spectrometry (UV-vis) and photoluminescence spectrophotometry (PL) demonstrate well dispersibility and excellent optical performance of Cu-ZnO hybrid nanoparticles both in organic and aqueous solvent. The X-ray photoelectron spectroscopy (XPS) confirms Cu1+ and Cu2+ in ZnO. The observation using Sudan red (III) as probe molecule reveals that the Cu-ZnO hybrid nanoparticles possess enhanced photocatalytic activity and stability which are promising for potential applications in photocatalysis.

Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

PubMed

Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

2003-09-22

The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

Thermodynamics of Pb(ii) and Zn(ii) binding to MT-3, a neurologically important metallothionein.

PubMed

Carpenter, M C; Shami Shah, A; DeSilva, S; Gleaton, A; Su, A; Goundie, B; Croteau, M L; Stevenson, M J; Wilcox, D E; Austin, R N

2016-06-01

Isothermal titration calorimetry (ITC) was used to quantify the thermodynamics of Pb(2+) and Zn(2+) binding to metallothionein-3 (MT-3). Pb(2+) binds to zinc-replete Zn7MT-3 displacing each zinc ion with a similar change in free energy (ΔG) and enthalpy (ΔH). EDTA chelation measurements of Zn7MT-3 and Pb7MT-3 reveal that both metal ions are extracted in a tri-phasic process, indicating that they bind to the protein in three populations with different binding thermodynamics. Metal binding is entropically favoured, with an enthalpic penalty that reflects the enthalpic cost of cysteine deprotonation accompanying thiolate ligation of the metal ions. These data indicate that Pb(2+) binding to both apo MT-3 and Zn7MT-3 is thermodynamically favourable, and implicate MT-3 in neuronal lead biochemistry.

Biocompatibility Assessment of Novel Bioresorbable Alloys Mg-Zn-Se and Mg-Zn-Cu for Endovascular Applications: In- Vitro Studies.

PubMed

Persaud-Sharma, Dharam; Budiansky, Noah; McGoron, Anthony J

2013-01-01

Previous studies have shown that using biodegradable magnesium alloys such as Mg-Zn and Mg-Zn-Al possess the appropriate mechanical properties and biocompatibility to serve in a multitude of biological applications ranging from endovascular to orthopedic and fixation devices. The objective of this study was to evaluate the biocompatibility of novel as-cast magnesium alloys Mg-1Zn-1Cu wt.% and Mg-1Zn-1Se wt.% as potential implantable biomedical materials, and compare their biologically effective properties to a binary Mg-Zn alloy. The cytotoxicity of these experimental alloys was evaluated using a tetrazolium based- MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) assay and a lactate dehydrogenase membrane integrity assay (LDH). The MTS assay was performed on extract solutions obtained from a 30-day period of alloy immersion and agitation in simulated body fluid to evaluate the major degradation products eluted from the alloy materials. Human foreskin fibroblast cell growth on the experimental magnesium alloys was evaluated for a 72 hour period, and cell death was quantified by measuring lactate dehydrogenase concentrations. Both Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. The Mg-Zn-Cu alloy was found to completely degrade within 72 hours, resulting in lower human foreskin fibroblast cell viability. The Mg-Zn-Se alloy was shown to be less cytotoxic than both the Mg-Zn-Cu and Mg-Zn alloys.

Biocompatibility Assessment of Novel Bioresorbable Alloys Mg-Zn-Se and Mg-Zn-Cu for Endovascular Applications: In- Vitro Studies

PubMed Central

Budiansky, Noah; McGoron, Anthony J.

2013-01-01

Previous studies have shown that using biodegradable magnesium alloys such as Mg-Zn and Mg-Zn-Al possess the appropriate mechanical properties and biocompatibility to serve in a multitude of biological applications ranging from endovascular to orthopedic and fixation devices. The objective of this study was to evaluate the biocompatibility of novel as-cast magnesium alloys Mg-1Zn-1Cu wt.% and Mg-1Zn-1Se wt.% as potential implantable biomedical materials, and compare their biologically effective properties to a binary Mg-Zn alloy. The cytotoxicity of these experimental alloys was evaluated using a tetrazolium based- MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) assay and a lactate dehydrogenase membrane integrity assay (LDH). The MTS assay was performed on extract solutions obtained from a 30-day period of alloy immersion and agitation in simulated body fluid to evaluate the major degradation products eluted from the alloy materials. Human foreskin fibroblast cell growth on the experimental magnesium alloys was evaluated for a 72 hour period, and cell death was quantified by measuring lactate dehydrogenase concentrations. Both Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. The Mg-Zn-Cu alloy was found to completely degrade within 72 hours, resulting in lower human foreskin fibroblast cell viability. The Mg-Zn-Se alloy was shown to be less cytotoxic than both the Mg-Zn-Cu and Mg-Zn alloys. PMID:24058329

Electrochemical EDTA recycling after soil washing of Pb, Zn and Cd contaminated soil.

PubMed

Pociecha, Maja; Kastelec, Damijana; Lestan, Domen

2011-08-30

Recycling of chelant decreases the cost of EDTA-based soil washing. Current methods, however, are not effective when the spent soil washing solution contains more than one contaminating metal. In this study, we applied electrochemical treatment of the washing solution obtained after EDTA extraction of Pb, Zn and Cd contaminated soil. A sacrificial Al anode and stainless steel cathode in a conventional electrolytic cell at pH 10 efficiently removed Pb from the solution. The method efficiency, specific electricity and Al consumption were significantly higher for solutions with a higher initial metal concentration. Partial replacement of NaCl with KNO(3) as an electrolyte (aggressive Cl(-) are required to prevent passivisation of the Al anode) prevented EDTA degradation during the electrolysis. The addition of FeCl(3) to the acidified washing solution prior to electrolysis improved Zn removal. Using the novel method 98, 73 and 66% of Pb, Zn and Cd, respectively, were removed, while 88% of EDTA was preserved in the treated washing solution. The recycled EDTA retained 86, 84 and 85% of Pb, Zn and Cd extraction potential from contaminated soil, respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Intrinsic point defects in off-stoichiometric Cu2ZnSnSe4: A neutron diffraction study

NASA Astrophysics Data System (ADS)

Gurieva, Galina; Valle Rios, Laura Elisa; Franz, Alexandra; Whitfield, Pamela; Schorr, Susan

2018-04-01

This work is an experimental study of intrinsic point defects in off-stoichiometric kesterite type CZTSe by means of neutron powder diffraction. We revealed the existence of copper vacancies (VCu), various cation anti site defects (CuZn, ZnCu, ZnSn, SnZn, and CuZn), as well as interstitials (Cui, Zni) in a wide range of off-stoichiometric polycrystalline powder samples synthesized by the solid state reaction. The results show that the point defects present in off-stoichiometric CZTSe agree with the off-stoichiometry type model, assuming certain cation substitutions accounting for charge balance. In addition to the known off-stoichiometry types A-H, new types (I-L) have been introduced. For the very first time, a correlation between the chemical composition of the CZTSe kesterite type phase and the occurring intrinsic point defects is presented. In addition to the off-stoichiometry type specific defects, the Cu/Zn disorder is always present in the CZTSe phase. In Cu-poor/Zn-rich CZTSe, a composition considered as the one that delivers the best photovoltaic performance, mainly copper vacancies, ZnCu and ZnSn anti sites are present. Also, this compositional region shows the lowest degree of Cu/Zn disorder.

Dilute electrodeposition of TiO2 and ZnO thin film memristors on Cu substrate

NASA Astrophysics Data System (ADS)

Fauzi, F. B.; Ani, M. H.; Herman, S. H.; Mohamed, M. A.

2018-03-01

Memristor has become one of the alternatives to replace the current memory technologies. Fabrication of titanium dioxide, TiO2 memristor has been extensively studied by using various deposition methods. However, recently more researches have been done to explore the compatibility of other transition metal oxide, TMO such as zinc oxide, ZnO to be used as the active layer of the memristor. This paper highlights the simple and easy-control electrodeposition to deposit titanium, Ti and zinc, Zn thin film at room temperature and subsequent thermal oxidation at 600 °C. Gold, Au was then sputtered as top electrode to create metal-insulator-metal, MIM sandwich of Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristors. The structural, morphological and memristive properties were characterized using Field Emission Scanning Electron Microscopy, FESEM, X-Ray Diffraction, XRD and current-voltage, I-V measurement. Both Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristivity were identified by the pinched hysteresis loop with resistive ratio of 1.2 and 1.08 respectively. Empirical study on diffusivity of Ti4+, Zn2+ and O2‑ ions in both metal oxides show that the metal vacancies were formed, thus giving rise to its memristivity. The electrodeposited Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristors demonstrate comparable performances to previous studies using other methods.

Electrodeposition and Characterization of Mn-Cu-Zn Alloys for Corrosion Protection Coating

NASA Astrophysics Data System (ADS)

Tsurtsumia, Gigla; Gogoli, David; Koiava, Nana; Kakhniashvili, Izolda; Jokhadze, Nunu; Lezhava, Tinatin; Nioradze, Nikoloz; Tatishvili, Dimitri

2017-12-01

Mn-Cu-Zn alloys were electrodeposited from sulphate bath, containing citrate or EDTA and their mixtures as complexing ligands. The influence of bath composition and deposition parameters on alloys composition, cathodic current efficiency and structural and electrochemical properties were studied. At a higher current density (≥ 37.5 A dm-2) a uniform surface deposit of Mn-Cu-Zn was obtained. Optimal pH of electrolyte (0.3 mol/dm3Mn2+ + 0.6 mol/dm3 (NH4)2SO4 +0.1 mol/dm3Zn2++0.005 mol/dm3 Cu2++ 0.05mol/dm3Na3Cit + 0.15mol/dm3 EDTA; t=300C; τ=20 min) for silvery, nonporous coating of Mn-Cu-Zn alloy was within 6.5-7.5; coating composition: 71-83% Mn, 6-7.8% Cu, 11.5-20% Zn, current efficiency up to 40%. XRD patterns revealed BCT (body centred tetragonal) γ-Mn solid phase solution (lattice constants a=2.68 Å c=3.59 Å). Corrosion measurements of deposited alloys were performed in aerated 3.5% NaCl solution. The corrosion current density (icorr) of the electrodeposited alloys on carbon steel was 10 times lower than corrosion rate of pure zinc and manganese coatings. Triple alloy coatings corrosion potential (Ecorr = -1140 mV vs. Ag/AgCl) preserved negative potential value longer (more than three months) compared to carbon steel substrate (Ecorr = -670 mV vs. Ag/AgCl). Tafel polarization curves taken on Mn-Cu-Zn alloy coating in aerated 3.5% NaCl solution did not show a typical passivation behaviour which can be explained by formation oflow solubility of adherent corrosion products on the alloy surface. Corrosion test of Mn-Cu-Zn electrocoating in chlorine environment shows that it is the best cathodic protective coating for a steel product.

Cu,Zn superoxide dismutase: cloning and analysis of the Taenia solium gene and Taenia crassiceps cDNA.

PubMed

Parra-Unda, Ricardo; Vaca-Paniagua, Felipe; Jiménez, Lucia; Landa, Abraham

2012-01-01

Cytosolic Cu,Zn superoxide dismutase (Cu,Zn-SOD) catalyzes the dismutation of superoxide (O(2)(-)) to oxygen and hydrogen peroxide (H(2)O(2)) and plays an important role in the establishment and survival of helminthes in their hosts. In this work, we describe the Taenia solium Cu,Zn-SOD gene (TsCu,Zn-SOD) and a Taenia crassiceps (TcCu,Zn-SOD) cDNA. TsCu,Zn-SOD gene that spans 2.841 kb, and has three exons and two introns; the splicing junctions follow the GT-AG rule. Analysis in silico of the gene revealed that the 5'-flanking region has three putative TATA and CCAAT boxes, and transcription factor binding sites for NF1 and AP1. The transcription start site was a C, located at 22 nucleotides upstream of the translation start codon (ATG). Southern blot analysis showed that TcCu,Zn-SOD and TsCu,Zn-SOD genes are encoded by a single copy. The deduced amino acid sequences of TsCu,Zn-SOD gene and TcCu,Zn-SOD cDNA reveal 98.47% of identity, and the characteristic motives, including the catalytic site and β-barrel structure of the Cu,Zn-SOD. Proteomic and immunohistochemical analysis indicated that Cu,Zn-SOD does not have isoforms, is distributed throughout the bladder wall and is concentrated in the tegument of T. solium and T. crassiceps cysticerci. Expression analysis revealed that TcCu,Zn-SOD mRNA and protein expression levels do not change in cysticerci, even upon exposure to O(2)(-) (0-3.8 nmol/min) and H(2)O(2) (0-2mM), suggesting that this gene is constitutively expressed in these parasites. Published by Elsevier Inc.

Solar Absorber Cu 2 ZnSnS 4 and its Parent Multilayers ZnS/SnS 2 /Cu 2 S Synthesized by Atomic Layer Deposition and Analyzed by X-ray Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baryshev, Sergey V.; Riha, Shannon C.; Zinovev, Alexander V.

2015-06-01

Presented here are results of x-ray photoelectron spectroscopy (XPS) on multilayers of metal-sulfide binaries ZnS, SnS2, and Cu2S grown by atomic layer deposition (ALD) on Si substrates, and of Cu2ZnSnS4 (CZTS) formed upon 450 °C annealing of the parent multilayer ZnS/SnS2/Cu2S. Survey and detailed spectral analysis of the multilayer ZnS/SnS2/Cu2S are presented step-wise, as each layer was sequentially added by ALD. The set of data is finalized with spectra of the resulting alloy CZTS. XPS analyses indicate significant mixing between SnS2 and Cu2S, which favors CZTS formation within the ALD approach.

Characterization of aerosols containing Zn, Pb, and Cl from an industrial region of Mexico City.

PubMed

Moffet, Ryan C; Desyaterik, Yury; Hopkins, Rebecca J; Tivanski, Alexei V; Gilles, Mary K; Wang, Y; Shutthanandan, V; Molina, Luisa T; Abraham, Rodrigo Gonzalez; Johnson, Kirsten S; Mugica, Violeta; Molina, Mario J; Laskin, Alexander; Prather, Kimberly A

2008-10-01

Recent ice core measurements show lead concentrations increasing since 1970, suggesting new nonautomobile-related sources of Pb are becoming important worldwide (1). Developing a full understanding of the major sources of Pb and other metals is critical to controlling these emissions. During the March, 2006 MILAGRO campaign, single particle measurements in Mexico City revealed the frequent appearance of particles internally mixed with Zn, Pb, Cl, and P. Pb concentrations were as high as 1.14 microg/m3 in PM10 and 0.76 microg/m3 in PM2.5. Real time measurements were used to select time periods of interest to perform offline analysis to obtain detailed aerosol speciation. Many Zn-rich particles had needle-like structures and were found to be composed of ZnO and/or Zn(NO3)2 x 6H2O. The internally mixed Pb-Zn-Cl particles represented as much as 73% of the fine mode particles (by number) in the morning hours between 2-5 am. The Pb-Zn-Cl particles were primarily in the submicrometer size range and typically mixed with elemental carbon suggesting a combustion source. The unique single particle chemical associations measured in this study closely match signatures indicative of waste incineration. Our findings also show these industrial emissions play an important role in heterogeneous processing of NO(y) species. Primary emissions of metal and sodium chloride particles emitted by the same source underwent heterogeneous transformations into nitrate particles as soon as photochemical production of nitric acid began each day at approximately 7 am.

Ultrafine particle and fine trace metal (As, Cd, Cu, Pb and Zn) pollution episodes induced by industrial emissions in Huelva, SW Spain

NASA Astrophysics Data System (ADS)

Fernández-Camacho, R.; Rodríguez, S.; de la Rosa, J.; Sánchez de la Campa, A. M.; Alastuey, A.; Querol, X.; González-Castanedo, Y.; Garcia-Orellana, I.; Nava, S.

2012-12-01

Urban air quality impairment by ultrafine particles has become a matter of concern due to the adverse effects on human health. Most of the studies of ultrafine particles in urban air quality have focused on vehicle exhaust emissions. We studied how industrial emissions contribute to ultrafine particle concentrations in downwind urban ambient air. This research is based on experimental data collected in the ambient air of the industrial city of Huelva (SW Spain) over April 2008-December 2009 period (particle number, gaseous pollutants and black carbon concentrations and levels and chemical composition of PM10 and PM2.5 with daily and hourly resolution). This city is affected by emissions from the second largest Cu-smelter in Europe, phosphoric acid and fertilizer production plants and an oil refinery and petrochemical plant. Industrial emissions are the main cause of ultrafine particle episodes. When vehicle exhaust emissions are the main source, ultrafine particles typically show (24-h mean) concentrations within the range 14,700-5000 cm-3 (50th-1st), with 60% of these linked to this source and 30% to industrial emissions. In contrast, when daily mean levels of N are within the range 50,000-25,500 cm-3 (100th-70th), industrial and vehicle exhaust emissions accounted for 49 and 30%, respectively. High concentrations of toxic trace metals (As, Cu, Cd, Zn and Pb) were recorded when the study city suffered fumigations of the Cu-smelter plumes (e.g. 10-25 ng m-3 As, 1-2 ng m-3 Cd and >105 cm-3 of ultrafine particles). Because of these industrial emissions, ultrafine particle concentrations during daylight are about two times higher than those observed in other European cities. Recently, ultrafine particle emissions in vehicle exhausts have been subject to limit values in a recent stage of the EURO standards. Industrial emissions should also be considered.

EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

NASA Astrophysics Data System (ADS)

Chevreux, Sylviane; Solari, Pier Lorenzo; Roudeau, Stéphane; Deves, Guillaume; Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis; Ortega, Richard

2009-11-01

Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

Towards Stable CuZnAl Slurry Catalysts for the Synthesis of Ethanol from Syngas

NASA Astrophysics Data System (ADS)

Dong, Weibing; Gao, Zhihua; Zhang, Qian; Huang, Wei

2018-07-01

A stable CuZnAl slurry catalyst for the synthesis of ethanol from syngas has been developed by adjusting the heat treatment conditions of the complete liquid-phase method. The activity evaluation results showed that the CuZnAl catalyst, when heat-treated under a high pressure and temperature, was a stable catalyst for the synthesis of ethanol. The selectivity of ethanol using the CuZnAl slurry catalyst, which was heat-treated at 553 K under 4.0 MPa, increased continuously with time and was stable at approximately 26.00% after 144 h. The characterization results indicated that the CuZnAl slurry catalyst heat-treated under high pressure conditions could facilitate the formation of a more perfect structure with a larger specific surface area. The prepared catalyst contained a balance of strong and weak acid sites, an appropriate form of Cu2O and a high Cu/Zn atomic ratio at the catalyst surface, providing its stability in ethanol synthesis from syngas.

The Cu2ZnSnSe4 thin films solar cells synthesized by electrodeposition route

NASA Astrophysics Data System (ADS)

Li, Ji; Ma, Tuteng; Wei, Ming; Liu, Weifeng; Jiang, Guoshun; Zhu, Changfei

2012-06-01

An electrodeposition route for preparing Cu2ZnSnSe4 thin films for thin film solar cell absorber layers is demonstrated. The Cu2ZnSnSe4 thin films are prepared by co-electrodeposition Cu-Zn-Sn metallic precursor and subsequently annealing in element selenium atmosphere. The structure, composition and optical properties of the films were investigated by X-ray diffraction (XRD), Raman spectrometry, energy dispersive spectrometry (EDS) and UV-VIS absorption spectroscopy. The Cu2ZnSnSe4 thin film with high crystalline quality was obtained, the band gap and absorption coefficient were 1.0 eV and 10-4 cm-1, which is quite suitable for solar cells fabrication. A solar cell with the structure of ZnO:Al/i-ZnO/CdS/Cu2ZnSnSe4/Mo/glass was fabricated and achieved an conversion efficiency of 1.7%.

Effect of Cu-Dopant on the Structural, Magnetic and Electrical Properties of ZnO

NASA Astrophysics Data System (ADS)

Aryanto, D.; Kurniawan, C.; Subhan, A.; Sudiro, T.; Sebayang, P.; Ginting, M.; Siregar, S. M. K.; Nasruddin, M. N.

2017-05-01

Zn1- x Cu x O (x = 0, 2, 3, and 4 at.%) was synthesized by using solid-state reaction technique. The ZnO and CuO powders were mixed and then milled by using high-speed shaker mill. The influence of Cu dopants on the structure, magnetic, and electrical properties was investigated by using XRD, VSM, and I-V and C-V measurements. The XRD analysis showed that the Zn1- x Cu x O had hexagonal wurtzite polycrystalline. The diffraction intensity decreased and the peak position shifted directly to a higher 2θ angle with increasing the dopant concentration. Furthermore, the lattice parameters decreased when the ZnO was doped with x = 0.04, which indicated that the crystal structure changed. The increase of Cu dopants was believed to affect the magnetic and electrical properties of ZnO.

Deposition of Cu-doped PbS thin films with low resistivity using DC sputtering

NASA Astrophysics Data System (ADS)

Soetedjo, Hariyadi; Siswanto, Bambang; Aziz, Ihwanul; Sudjatmoko

2018-03-01

Investigation of the electrical resistivity of Cu-doped PbS thin films has been carried out. The films were prepared using a DC sputtering technique. The doping was achieved by introducing the Cu dopant plate material directly on the surface of the PbS sputtering target plate. SEM-EDX data shows the Cu concentration in the PbS film to be proportional to the Cu plate diameter. The XRD pattern indicates the film is in crystalline cubic form. The Hall effect measurement shows that Cu doping yields an increase in the carrier concentration to 3.55 × 1019 cm-3 and a significant decrease in electrical resistivity. The lowest resistivity obtained was 0.13 Ωcm for a Cu concentration of 18.5%. Preferential orientation of (1 1 1) and (2 0 0) occurs during deposition.

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions.

PubMed

Lassabatere, Laurent; Spadini, Lorenzo; Delolme, Cécile; Février, Laureline; Galvez Cloutier, Rosa; Winiarski, Thierry

2007-11-01

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.

Electron paramagnetic resonance in Cu-doped ZnO

NASA Astrophysics Data System (ADS)

Buchheit, R.; Acosta-Humánez, F.; Almanza, O.

2016-04-01

In this work, ZnO and Cu-doped ZnO nanoparticles (Zn1-xCuxO, x = 3%), with a calcination temperature of 500∘C were synthesized using the sol-gel method. The particles were analyzed using atomic absorption spectroscopy (AAS), X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) at X-band, measurement in a temperature range from 90 K to room temperature. AAS confirmed a good correspondence between the experimental doping concentration and the theoretical value. XRD reveals the presence of ZnO phase in hexagonal wurtzite structure and a nanoparticle size for the samples synthesized. EPR spectroscopy shows the presence of point defects in both samples with g-values of g = 1.959 for shallow donors and g = 2.004 for ionized vacancies. It is important when these materials are required have been used as catalysts, as suggested that it is not necessary prepare them at higher temperature. A simulation of the Cu EPR signal using an anisotropic spin Hamiltonian was performed and showed good coincidence with the experimental spectra. It was shown that Cu2+ ions enter interstitial octahedral sites of orthorhombic symmetry in the wurtzite crystal structure. Temperature dependence of the EPR linewidth and signal intensity shows a paramagnetic behavior of the sample in the measurement range. A Néel temperature TN = 78 ± 19 K was determined.

Comparative of Quercus spp. and Salix spp. for phytoremediation of Pb/Zn mine tailings.

PubMed

Shi, Xiang; Wang, Shufeng; Sun, Haijing; Chen, Yitai; Wang, Dongxue; Pan, Hongwei; Zou, Yazhu; Liu, Jianfeng; Zheng, Linyu; Zhao, Xiulian; Jiang, Zeping

2017-02-01

A pot experiment was conducted to evaluate the feasibility of using tree seedlings for the phytoremediation of lead/zinc (Pb/Zn) mine tailings. Seedlings of three Quercus spp. (Q. shumardii, Q. phellos, and Q. virginiana) and rooted cuttings of two Salix spp. (S. matsudana and S. integra) were transplanted into pots containing 50 and 100 % Pb/Zn mine tailings to evaluate their tolerance of heavy metals. The five species showed different tolerance levels to the Pb/Zn tailings treatments. Q. virginiana was highly tolerant to heavy metals and grew normally in the Pb/Zn tailings. The root systems showed marked differences between the Quercus spp. and Salix spp., indicating that different mechanisms operated to confer tolerance of heavy metals. The maximum efficiency of photosystem II photochemistry value of the five species showed no differences among the treatments, except for Q. shumardii. All species showed low metal translocation factors (TFs). However, S. integra had significantly higher TF values for Zn (1.42-2.18) and cadmium (1.03-1.45) than did the other species. In this respect, Q. virginiana showed the highest tolerance and a low TF, implying that it is a candidate for phytostabilization of mine tailings in southern China. S. integra may be useful for phytoextraction of tailings in temperate regions.

Continuous biosorption of Pb/Cu and Pb/Cd in fixed-bed column using algae Gelidium and granulated agar extraction algal waste.

PubMed

Vilar, Vítor J P; Loureiro, José M; Botelho, Cidália M S; Boaventura, Rui A R

2008-06-15

Continuous metal ions biosorption from Pb/Cu and Pb/Cd solutions onto seaweed Gelidium sesquipedale and a composite material prepared from an industrial algal waste was performed in a packed bed column. A binary Langmuir equation describes well the equilibrium data and indicates a good adsorption capacity. In the sorption process, Cd and Cu break through the column faster than Pb due to its lower affinity for the biosorbent. An overshoot in the outlet Cd concentration was observed and explained by competitive adsorption between Pb and Cd, whereby the higher Pb affinity for the biosorbent displaces bound Cd ions. A small overshoot happens for Cu adsorption in the presence of Pb ions. Desorption using 0.1 M HNO3 as eluant, was 100% effective. A mass transfer model for the adsorption and desorption processes, considering an external and intraparticle film resistance, adequately simulates the column performance. A binary Langmuir equation was used to describe equilibrium for the saturation process and a mass action law for the desorption process. Elution process is defined as an ion exchange mechanism, between protons and metal ions.

Thermoelectric Properties of Bi₂Te₃: CuI and the Effect of Its Doping with Pb Atoms.

PubMed

Han, Mi-Kyung; Jin, Yingshi; Lee, Da-Hee; Kim, Sung-Jin

2017-10-26

In order to understand the effect of Pb-CuI co-doping on the thermoelectric performance of Bi₂Te₃, n -type Bi₂Te₃ co-doped with x at % CuI and 1/2 x at % Pb ( x = 0, 0.01, 0.03, 0.05, 0.07, and 0.10) were prepared via high temperature solid state reaction and consolidated using spark plasma sintering. Electron and thermal transport properties, i.e., electrical conductivity, carrier concentration, Hall mobility, Seebeck coefficient, and thermal conductivity, of CuI-Pb co-doped Bi₂Te₃ were measured in the temperature range from 300 K to 523 K, and compared to corresponding x % of CuI-doped Bi₂Te₃ and undoped Bi₂Te₃. The addition of a small amount of Pb significantly decreased the carrier concentration, which could be attributed to the holes from Pb atoms, thus the CuI-Pb co-doped samples show a lower electrical conductivity and a higher Seebeck coefficient when compared to CuI-doped samples with similar x values. The incorporation of Pb into CuI-doped Bi₂Te₃ rarely changed the power factor because of the trade-off relationship between the electrical conductivity and the Seebeck coefficient. The total thermal conductivity(κ tot ) of co-doped samples (κ tot ~ 1.4 W/m∙K at 300 K) is slightly lower than that of 1% CuI-doped Bi₂Te₃ (κ tot ~ 1.5 W/m∙K at 300 K) and undoped Bi₂Te₃ (κ tot ~ 1.6 W/m∙K at 300 K) due to the alloy scattering. The 1% CuI-Pb co-doped Bi₂Te 3 sample shows the highest ZT value of 0.96 at 370 K. All data on electrical and thermal transport properties suggest that the thermoelectric properties of Bi₂Te 3 and its operating temperature can be controlled by co-doping.

Accumulation of Cr, Cd, Pb, Cu, and Zn by plants in tanning sludge storage sites: opportunities for contamination bioindication and phytoremediation.

PubMed

Yuan, Yongqiang; Yu, Shen; Bañuelos, G S; He, Yunfeng

2016-11-01

Tanning sludge enriched with high concentrations of Cr and other metals has adverse effects on the environment. Plants growing in the metalliferous soils may have the ability to cope with high metal concentrations. This study focuses on potentials of using native plants for bioindication and/or phytoremediation of Cr-contaminated sites. In the study, we characterized plants and soils from six tanning sludge storage sites. Soil in these sites exhibited toxic levels of Cr (averaged 16,492 mg kg -1 ) and other metals (e.g., 48.3 mg Cu kg -1 , 2370 mg Zn kg -1 , 44.9 mg Pb kg -1 , and 0.59 mg Cd kg -1 ). Different metal tolerance and accumulation patterns were observed among the sampled plant species. Phragmites australis, Zephyranthes candida, Cynodon dactylon, and Alternanthera philoxeroides accumulated moderate-high concentrations of Cr and other metals, which could make them good bioindicators of heavy metal pollution. High Cr and other metal concentrations (e.g., Cd and Pb) were found in Chenopodium rubrum (372 mg Cr kg -1 ), Aster subulatus (310 mg Cr kg -1 ), and Brassica chinensis (300 mg Cr kg -1 ), being considered as metal accumulators. In addition, Nerium indicum and Z. candida were able to tolerate high concentrations of Cr and other metals, and they may be used as preferable pioneer species to grow or use for restoration in Cr-contaminated sites. This study can be useful for establishing guidelines to select the most suitable plant species to revegetate and remediate metals in tanning sludge-contaminated fields.

A facile green antisolvent approach to Cu2+-doped ZnO nanocrystals with visible-light-responsive photoactivities.

PubMed

Lu, Yi-Hsuan; Lin, Wei-Hao; Yang, Chao-Yao; Chiu, Yi-Hsuan; Pu, Ying-Chih; Lee, Min-Han; Tseng, Yuan-Chieh; Hsu, Yung-Jung

2014-08-07

An environmentally benign antisolvent method has been developed to prepare Cu(2+)-doped ZnO nanocrystals with controllable dopant concentrations. A room temperature ionic liquid, known as a deep eutectic solvent (DES), was used as the solvent to dissolve ZnO powders. Upon the introduction of the ZnO-containing DES into a bad solvent which shows no solvation to ZnO, ZnO was precipitated and grown due to the dramatic decrease of solubility. By adding Cu(2+) ions to the bad solvent, the growth of ZnO from the antisolvent process was accompanied by Cu(2+) introduction, resulting in the formation of Cu(2+)-doped ZnO nanocrystals. The as-prepared Cu(2+)-doped ZnO showed an additional absorption band in the visible range (400-800 nm), which conduced to an improvement in the overall photon harvesting efficiency. Time-resolved photoluminescence spectra, together with the photovoltage information, suggested that the doped Cu(2+) may otherwise trap photoexcited electrons during the charge transfer process, inevitably depressing the photoconversion efficiency. The photoactivity of Cu(2+)-doped ZnO nanocrystals for photoelectrochemical water oxidation was effectively enhanced in the visible region, which achieved the highest at 2.0 at% of Cu(2+). A further increase in the Cu(2+) concentration however led to a decrease in the photocatalytic performance, which was ascribed to the significant carrier trapping caused by the increased states given by excessive Cu(2+). The photocurrent action spectra illustrated that the enhanced photoactivity of the Cu(2+)-doped ZnO nanocrystals was mainly due to the improved visible photon harvesting achieved by Cu(2+) doping. These results may facilitate the use of transition metal ion-doped ZnO in other photoconversion applications, such as ZnO based dye-sensitized solar cells and magnetism-assisted photocatalytic systems.

Complete transformation of ZnO and CuO nanoparticles in culture medium and lymphocyte cells during toxicity testing.

PubMed

Ivask, Angela; Scheckel, Kirk G; Kapruwan, Pankaj; Stone, Vicki; Yin, Hong; Voelcker, Nicolas H; Lombi, Enzo

2017-03-01

Here, we present evidence on complete transformation of ZnO and CuO nanoparticles, which are among the most heavily studied metal oxide particles, during 24 h in vitro toxicological testing with human T-lymphocytes. Synchrotron radiation-based X-ray absorption near edge structure (XANES) spectroscopy results revealed that Zn speciation profiles of 30 nm and 80 nm ZnO nanoparticles, and ZnSO 4 - exposed cells were almost identical with the prevailing species being Zn-cysteine. This suggests that ZnO nanoparticles are rapidly transformed during a standard in vitro toxicological assay, and are sequestered intracellularly, analogously to soluble Zn. Complete transformation of ZnO in the test conditions was further supported by almost identical Zn spectra in medium to which ZnO nanoparticles or ZnSO 4 was added. Likewise, Cu XANES spectra for CuO and CuSO 4 -exposed cells and cell culture media were similar. These results together with our observation on similar toxicological profiles of ZnO and soluble Zn, and CuO and soluble Cu, underline the importance of dissolution and subsequent transformation of ZnO and CuO nanoparticles during toxicological testing and provide evidence that the nano-specific effect of ZnO and CuO nanoparticles is negligible in this system. We strongly suggest to account for this aspect when interpreting the toxicological results of ZnO and CuO nanoparticles.

Cu0-loaded SBA-15@ZnO with improved electrical properties and affinity towards hydrogen

NASA Astrophysics Data System (ADS)

Bouazizi, N.; Louhichi, S.; Ouargli, R.; Bargougui, R.; Vieillard, J.; Derf, F. Le; Azzouz, A.

2017-05-01

A core-shell material was prepared using SBA-15 crystallites as cores for the growth of a ZnO shell, followed by Cu0 dispersion. The resulting Cu/SBA-15@ZnO nanostructure displayed higher specific surface area (SSA) and higher number of smaller pores as compared to the starting materials. Dispersion of fine Cu0NPs induced a compaction of the host matrice and a marked decay of the hydrophilic character, explained in terms of the involvement of terminal hydroxyl groups in competitive sbnd HO:Cu interaction at the expense of H-bridges with water. Heating at 400-450 °C seems to trigger ZnO dehydroxylation with possible self-polycondensation and/or the formation of Si-O-Zn bridges. This is an additional explanation of the significant SSA increase and decrease in the average pore diameter. Both ZnO and Cu0NP incorporation induced shifts in the UV-vis absorption band towards higher wavelengths, indicating a decrease in the optical band gap energy and an improvement of the conductance properties. As compared to ZnO, Cu0NPs produced stronger improvement of the conductance, which was found to increase with higher frequencies. Cu/SBA-15@ZnO also displayed higher affinity towards hydrogen as compared to SBA-15@ZnO and SBA-15 at ambient conditions. These outstanding properties combined to an appreciable thermal stability are worth to be prone to deeper investigations, because they can open promising prospects for Cu/SBA-15@ZnO as sensor, electrode material, electrocatalyst and/or hydrogen capture matrice.

Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

DOE PAGES

Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; ...

2016-10-17

Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level ofmore » Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.« less

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Weidong; Cao, Di; Jin, Yunxue

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

DOE PAGES

Gao, Weidong; Cao, Di; Jin, Yunxue; ...

2018-04-18

Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

Geology, S-Pb isotopes, and 40Ar/39Ar geochronology of the Zhaxikang Sb-Pb-Zn-Ag deposit in Southern Tibet: implications for multiple mineralization events at Zhaxikang

NASA Astrophysics Data System (ADS)

Sun, Xiang; Zheng, Youye; Pirajno, Franco; McCuaig, T. Campbell; Yu, Miao; Xia, Shenlan; Song, Qingjie; Chang, Huifang

2018-03-01

Several Au, Sb, Sb-Au, Pb-Zn, and Sb-Pb-Zn-Ag deposits are present throughout the North Himalaya in southern Tibet, China. The largest Sb-Pb-Zn-Ag deposit is Zhaxikang (18 Mt at 0.6 wt% Sb, 2.0 wt% Pb, 3.5 wt% Zn, and 78 g/t Ag). Zhaxikang veins are hosted within N-S trending faults, which crosscut the Early-Middle Jurassic Ridang Formation consisting of shale interbedded with sandstone and limestone deposited on a passive continental margin. Ore paragenesis indicates that Zhaxikang mineralization occurred in two main phases composed of six total stages. The initial phase was characterized by assemblages of fine-grained Mn-Fe carbonate + arsenopyrite + pyrite + sphalerite (stage 1), followed by relatively coarse-grained Mn-Fe carbonate + Fe-rich sphalerite + galena + pyrite (stage 2). The second phase was marked by assemblages of quartz + pyrite + Fe-poor sphalerite and Ag-rich galena + tetrahedrite + sericite (stage 3), quartz + Sb-Pb sulfosalt minerals mainly composed of boulangerite and jamesonite (stage 4), quartz + stibnite ± cinnabar (stage 5), and quartz ± calcite (stage 6). Sulfides of stage 2 have δ34SV-CDT of 8.4-12.0‰, 206Pb/204Pb ratios of 19.648 to 19.659, 207Pb/204Pb ratios of 15.788 to 15.812, and 208Pb/204Pb ratios of 40.035 to 40.153. Sulfides of stage 3 have similar δ34SV-CDT of 6.1-11.2‰ and relatively more radiogenic lead isotopes (206Pb/204Pb = 19.683-19.792). Stage 4 Sb-Pb sulfosalt minerals have δ34SV-CDT of 5.0-7.2‰ and even more radiogenic lead (206Pb/204Pb = 19.811-19.981). By contrast, stibnite of stage 5 has δ34SV-CDT of 4.5-7.8‰ and less radiogenic lead (206Pb/204Pb = 18.880-18.974). Taken together with the geological observations that the Pb-Zn-bearing Mn-Fe carbonate veins were crosscut by various types of quartz veins, sphalerite and galena of stage 2 underwent dissolution and remobilization, and that Sb-Pb(-Fe) sulfosalts formed at the expense of Pb from stage 2 galena and of Fe from stage 2 sphalerite, we argue that

Visible light-driven photocatalytic H{sub 2}-generation activity of CuS/ZnS composite particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Liang; Chen, Hua; Huang, Jianhua, E-mail: jhhuang@zstu.edu.cn

2015-04-15

Highlights: • Preparation of CuS/ZnS composite photocatalyst by cation-exchange reaction. • Visible light photocatalytic activity for H{sub 2} evolution without cocatalyst. • The H{sub 2}-evolution rate from water splitting depends on the CuS content. • The highest rate of H{sub 2} evolution is obtained with CuS (0.5 mol%)/ZnS composite. - Abstract: CuS/ZnS composite particles with diameter of 200–400 nm were successfully prepared by a simple cation-exchange reaction using ZnS spheres as a precursor. CuS nanoparticles with a few nanometers in diameter were observed on the surface of composite particles. The synthesized CuS/ZnS composite particles showed photocatalytic property effective for H{submore » 2} evolution from an aqueous Na{sub 2}S and Na{sub 2}SO{sub 3} solution under visible light irradiation without any cocatalysts. The rate of H{sub 2} generation was found to be strongly dependent on the CuS content. The highest rate of H{sub 2} evolution reached 695.7 μmol h{sup −1} g{sup −1}, which was almost 7 times as high as that of the mechanical mixture of CuS and ZnS. The enhancement in the photocatalytic activity of CuS/ZnS composite particles is supposed to be due to the direct interfacial charge transfer of the CuS/ZnS heterojunction.« less

ZnO/Cu nanocomposite: a platform for direct electrochemistry of enzymes and biosensing applications.

PubMed

Yang, Chi; Xu, Chunxiang; Wang, Xuemei

2012-03-06

Unique structured nanomaterials can facilitate the direct electron transfer between redox proteins and the electrodes. Here, in situ directed growth on an electrode of a ZnO/Cu nanocomposite was prepared by a simple corrosion approach, which enables robust mechanical adhesion and electrical contact between the nanostructured ZnO and the electrodes. This is great help to realize the direct electron transfer between the electrode surface and the redox protein. SEM images demonstrate that the morphology of the ZnO/Cu nanocomposite has a large specific surface area, which is favorable to immobilize the biomolecules and construct biosensors. Using glucose oxidase (GOx) as a model, this ZnO/Cu nanocomposite is employed for immobilization of GOx and the construction of the glucose biosensor. Direct electron transfer of GOx is achieved at ZnO/Cu nanocomposite with a high heterogeneous electron transfer rate constant of 0.67 ± 0.06 s(-1). Such ZnO/Cu nanocomposite provides a good matrix for direct electrochemistry of enzymes and mediator-free enzymatic biosensors.

Synthesis of ZnO/CuO and TiO{sub 2}/CuO nanocomposites for light and ultrasound assisted degradation of a textile dye in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muzakki, Afifah; Shabrany, Hesni; Saleh, Rosari, E-mail: rosari.saleh@gmail.com, E-mail: rosari.saleh@ui.ac.id

2016-04-19

ZnO/CuO and TiO2/CuO nanocomposites with different Zn/Cu and Ti/Cu ratios were prepared using sol-gel method. The obtained composite samples were used as catalyst. Methylene blue was used as a model of textile dye to evaluate their photocatalytic, sonocatalytic and photosonocatalytic activities. X-ray diffraction and energy dispersive X- ray analysis confirmed that only monoclinic CuO and hexagonal wurtzite ZnO structures are present in ZnO/CuO nanocomposites, while in TiO2/CuO nanocomposites monoclinic CuO and anatase TiO2 structures were observed. The degradation of methylene blue indicated that the incorporation of CuO in ZnO/CuO and TiO2/CuO nanocomposites exhibited an appreciable higher photocatalytic activity, which wasmore » mainly attributed to the extended photoresponding range and more light energy could be utilized than pure ZnO and TiO2.« less

Effects of Cu(2+) and Zn(2+) on growth and physiological characteristics of green algae, Cladophora.

PubMed

Cao, De-ju; Xie, Pan-pan; Deng, Juan-wei; Zhang, Hui-min; Ma, Ru-xiao; Liu, Cheng; Liu, Ren-jing; Liang, Yue-gan; Li, Hao; Shi, Xiao-dong

2015-11-01

Effects of various concentrations of Cu(2+) and Zn(2+) (0.0, 0.1, 0.25, 0.5, or 1.0 mg/L) on the growth, malondialdehyde (MDA), the intracellular calcium, and physiological characteristics of green algae, Cladophora, were investigated. Low Zn(2+) concentrations accelerated the growth of Cladophora, whereas Zn(2+) concentration increases to 0.25 mg/L inhibited its growth. Cu(2+) greatly influences Cladophora growth. The photosynthesis of Cladophora decreased under Zn(2+) and Cu(2+) stress. Cu(2+) and Zn(2+) treatment affected the content of total soluble sugar in Cladophora and has small increases in its protein content. Zn(2+) induced the intracellular calcium release, and copper induced the intracellular calcium increases in Cladophora. Exposure to Cu(2+) and Zn(2+) induces MDA in Cladophora. The stress concent of Cu(2+) was strictly correlated with the total soluble sugar content, Chla+Chlb, and MDA in Cladophora, and the stress concent of Zn(2+) was strictly correlated with the relative growth rate (RGR) and MDA of Cladophora.

Copper doping of ZnO crystals by transmutation of 64Zn to 65Cu: An electron paramagnetic resonance and gamma spectroscopy study

NASA Astrophysics Data System (ADS)

Recker, M. C.; McClory, J. W.; Holston, M. S.; Golden, E. M.; Giles, N. C.; Halliburton, L. E.

2014-06-01

Transmutation of 64Zn to 65Cu has been observed in a ZnO crystal irradiated with neutrons. The crystal was characterized with electron paramagnetic resonance (EPR) before and after the irradiation and with gamma spectroscopy after the irradiation. Major features in the gamma spectrum of the neutron-irradiated crystal included the primary 1115.5 keV gamma ray from the 65Zn decay and the positron annihilation peak at 511 keV. Their presence confirmed the successful transmutation of 64Zn nuclei to 65Cu. Additional direct evidence for transmutation was obtained from the EPR of Cu2+ ions (where 63Cu and 65Cu hyperfine lines are easily resolved). A spectrum from isolated Cu2+ (3d9) ions acquired after the neutron irradiation showed only hyperfine lines from 65Cu nuclei. The absence of 63Cu lines in this Cu2+ spectrum left no doubt that the observed 65Cu signals were due to transmuted 65Cu nuclei created as a result of the neutron irradiation. Small concentrations of copper, in the form of Cu+-H complexes, were inadvertently present in our as-grown ZnO crystal. These Cu+-H complexes are not affected by the neutron irradiation, but they dissociate when a crystal is heated to 900 °C. This behavior allowed EPR to distinguish between the copper initially in the crystal and the copper subsequently produced by the neutron irradiation. In addition to transmutation, a second major effect of the neutron irradiation was the formation of zinc and oxygen vacancies by displacement. These vacancies were observed with EPR.

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during

Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata.

PubMed

Aruoja, Villem; Dubourguier, Henri-Charles; Kasemets, Kaja; Kahru, Anne

2009-02-01

Toxicities of ZnO, TiO2 and CuO nanoparticles to Pseudokirchneriella subcapitata were determined using OECD 201 algal growth inhibition test taking in account potential shading of light. The results showed that the shading effect by nanoparticles was negligible. ZnO nanoparticles were most toxic followed by nano CuO and nano TiO2. The toxicities of bulk and nano ZnO particles were both similar to that of ZnSO4 (72 h EC50 approximately 0.04 mg Zn/l). Thus, in this low concentration range the toxicity was attributed solely to solubilized Zn2+ ions. Bulk TiO2 (EC50=35.9 mg Ti/l) and bulk CuO (EC50=11.55 mg Cu/l) were less toxic than their nano formulations (EC50=5.83 mg Ti/l and 0.71 mg Cu/l). NOEC (no-observed-effect-concentrations) that may be used for risk assessment purposes for bulk and nano ZnO did not differ (approximately 0.02 mg Zn/l). NOEC for nano CuO was 0.42 mg Cu/l and for bulk CuO 8.03 mg Cu/l. For nano TiO2 the NOEC was 0.98 mg Ti/l and for bulk TiO2 10.1 mg Ti/l. Nano TiO2 formed characteristic aggregates entrapping algal cells that may contribute to the toxic effect of nano TiO2 to algae. At 72 h EC50 values of nano CuO and CuO, 25% of copper from nano CuO was bioavailable and only 0.18% of copper from bulk CuO. Thus, according to recombinant bacterial and yeast Cu-sensors, copper from nano CuO was 141-fold more bioavailable than from bulk CuO. Also, toxic effects of Cu oxides to algae were due to bioavailable copper ions. To our knowledge, this is one of the first systematic studies on effects of metal oxide nanoparticles on algal growth and the first describing toxic effects of nano CuO towards algae.

Effects of annealing on the ferromagnetism and photoluminescence of Cu-doped ZnO nanowires.

PubMed

Xu, H J; Zhu, H C; Shan, X D; Liu, Y X; Gao, J Y; Zhang, X Z; Zhang, J M; Wang, P W; Hou, Y M; Yu, D P

2010-01-13

Room temperature ferromagnetic Cu-doped ZnO nanowires have been synthesized using the chemical vapor deposition method. By combining structural characterizations and comparative annealing experiments, it has been found that both extrinsic (CuO nanoparticles) and intrinsic (Zn(1-x)Cu(x)O nanowires) sources are responsible for the observed ferromagnetic ordering of the as-grown samples. As regards the former, annealing in Zn vapor led to a dramatic decrease of the ferromagnetism. For the latter, a reversible switching of the ferromagnetism was observed with sequential annealings in Zn vapor and oxygen ambience respectively, which agreed well with previous reports for Cu-doped ZnO films. In addition, we have for the first time observed low temperature photoluminescence changed with magnetic properties upon annealing in different conditions, which revealed the crucial role played by interstitial zinc in directly mediating high T(c) ferromagnetism and indirectly modulating the Cu-related structured green emission via different charge transfer transitions.

Synthesis of BiPbSrCaCuO superconductor

DOEpatents

Hults, W.L.; Kubat-Martin, K.A.; Salazar, K.V.; Phillips, D.S.; Peterson, D.E.

1994-04-05

A process and a precursor composition for preparing a lead-doped bismuth-strontium-calcium-copper oxide superconductor of the formula Bi[sub a]Pb[sub b]Sr[sub c]Ca[sub d]Cu[sub e]O[sub f] wherein a is from about 1.7 to about 1.9, b is from about 0.3 to about 0.45, c is from about 1.6 to about 2.2, d is from about 1.6 to about 2.2, e is from about 2.97 to about 3.2 and f is 10[+-]z by reacting a mixture of Bi[sub 4]Sr[sub 3]Ca[sub 3]Cu[sub 4]O[sub 16[+-]z], an alkaline earth metal cuprate, e.g., Sr[sub 9]Ca[sub 5]Cu[sub 24]O[sub 41], and an alkaline earth metal plumbate, e.g., Ca[sub 2[minus]x]Sr[sub x]PbO[sub 4] wherein x is about 0.5, is disclosed.

Synthesis of BiPbSrCaCuO superconductor

DOEpatents

Hults, William L.; Kubat-Martin, Kimberly A.; Salazar, Kenneth V.; Phillips, David S.; Peterson, Dean E.

1994-01-01

A process and a precursor composition for preparing a lead-doped bismuth-strontium-calcium-copper oxide superconductor of the formula Bi.sub.a Pb.sub.b Sr.sub.c Ca.sub.d Cu.sub.e O.sub.f wherein a is from about 1.7 to about 1.9, b is from about 0.3 to about 0.45, c is from about 1.6 to about 2.2, d is from about 1.6 to about 2.2, e is from about 2.97 to about 3.2 and f is 10.+-.z by reacting a mixture of Bi.sub.4 Sr.sub.3 Ca.sub.3 Cu.sub.4 O.sub.16.+-.z, an alkaline earth metal cuprate, e.g., Sr.sub.9 Ca.sub.5 Cu.sub.24 O.sub.41, and an alkaline earth metal plumbate, e.g., Ca.sub.2-x Sr.sub.x PbO.sub.4 wherein x is about 0.5, is disclosed.

Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions

NASA Astrophysics Data System (ADS)

Li, Yuan; Audétat, Andreas

2012-11-01

The partitioning of 15 major to trace metals between monosulfide solid solution (MSS), sulfide liquid (SL) and mafic silicate melt (SM) was determined in piston-cylinder experiments performed at 1175-1300 °C, 1.5-3.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the quartz-fayalite-magnetite fO2 buffer, which conditions are representative of partial melting in the upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a natural, amphibole-rich mantle source rock, resulting in hydrous (˜5 wt% H2O) basanitic melts similar to low-degree partial melts of metasomatized mantle, whereas the major element composition of the starting sulfide (˜52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of sulfides in this environment. SL/SM partition coefficients are high (≥100) for Au, Ni, Cu, Ag, Bi, intermediate (1-100) for Co, Pb, Sn, Sb (±As, Mo), and low (≤1) for the remaining elements. MSS/SM partition coefficients are generally lower than SL/SM partition coefficients and are high (≥100) for Ni, Cu, Au, intermediate (1-100) for Co, Ag (±Bi, Mo), and low (≤1) for the remaining elements. Most sulfide-silicate melt partition coefficients vary as a function of fO2, with Mo, Bi, As (±W) varying by a factor >10 over the investigated fO2 range, Sb, Ag, Sn (±V) varying by a factor of 3-10, and Pb, Cu, Ni, Co, Au, Zn, Mn varying by a factor of 3-10. The partitioning data were used to model the behavior of Cu, Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive MORB and arc magmas. Sulfide phase relationships and comparison of the modeling results with reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the dominant sulfide in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and residual sulfides may decrease with increasing degree of

The accumulation of elements in plants growing spontaneously on small heaps left by the historical Zn-Pb ore mining.

PubMed

Stefanowicz, Anna M; Stanek, Małgorzata; Woch, Marcin W; Kapusta, Paweł

2016-04-01

The study evaluated the levels of nine metals, namely Ca, Cd, Fe, K, Mg, Mn, Pb, Tl, and Zn, in soils and tissues of ten plant species growing spontaneously on heaps left by historical mining for Zn-Pb ores. The concentrations of Cd, Pb, Tl, and Zn in heap soils were much higher than in control soils. Plants growing on heaps accumulated excessive amounts of these elements in tissues, on average 1.3-52 mg Cd kg(-1), 9.4-254 mg Pb kg(-1), 0.06-23 mg Tl kg(-1) and 134-1479 mg Zn kg(-1) in comparison to 0.5-1.1 mg Cd kg(-1), 2.1-11 mg Pb kg(-1), 0.02-0.06 mg Tl kg(-1), and 23-124 mg Zn kg(-1) in control plants. The highest concentrations of Cd, Pb, and Zn were found in the roots of Euphorbia cyparissias, Fragaria vesca, and Potentilla arenaria, and Tl in Plantago lanceolata. Many species growing on heaps were enriched in K and Mg, and depleted in Ca, Fe, and Mn. The concentrations of all elements in plant tissues were dependent on species, organ (root vs. shoot), and species-organ interactions. Average concentrations of Ca, K, and Mg were generally higher in shoots than in roots or similar in the two organs, whereas Cd, Fe, Pb, Tl, and Zn were accumulated predominantly in the roots. Our results imply that heaps left by historical mining for Zn-Pb ores may pose a potential threat to the environment and human health.

Growth of Cu2ZnSnSe4 Film under Controllable Se Vapor Composition and Impact of Low Cu Content on Solar Cell Efficiency.

PubMed

Li, Jianjun; Wang, Hongxia; Wu, Li; Chen, Cheng; Zhou, Zhiqiang; Liu, Fangfang; Sun, Yun; Han, Junbo; Zhang, Yi

2016-04-27

It is a challenge to fabricate high quality Cu2ZnSnSe4 (CZTSe) film with low Cu content (Cu/(Zn + Sn) < 0.8). In this work, the growth mechanisms of CZTSe films under different Se vapor composition are investigated by DC-sputtering and a postselenization approach. The composition of Se vapor has important influence on the compactability of the films and the diffusion of elements in the CZTSe films. By adjusting the composition of Se vapor during the selenization process, an optimized two step selenization process is proposed and highly crystallized CZTSe film with low Cu content (Cu/(Zn + Sn) = 0.75) is obtained. Further study of the effect of Cu content on the morphology and photovoltaic performance of the corresponding CZTSe solar cells has shown that the roughness of the CZTSe absorber film increases when Cu content decreases. As a consequence, the reflection loss of CZTSe solar cells reduces dramatically and the short circuit current density of the cells improve from 34.7 mA/cm(2) for Cu/(Zn + Sn) = 0.88 to 38.5 mA/cm(2) for Cu/(Zn + Sn) = 0.75. In addition, the CZTSe solar cells with low Cu content show longer minority carrier lifetime and higher open circuit voltage than the high Cu content devices. A champion performance CZTSe solar cell with 10.4% efficiency is fabricated with Cu/(Zn + Sn) = 0.75 in the CZTSe film without antireflection coating.

X-ray photoemission studies of Zn doped Cu 1- xTl xBa 2Ca 2Cu 3- yZn yO 10- δ ( y = 0, 2.65) superconductors

NASA Astrophysics Data System (ADS)

Khan, Nawazish A.; Mumtaz, M.; Ahadian, M. M.; Iraji-zad, Azam

2007-03-01

The X-ray photoemission (XPS) measurements of Cu 1- xTl xBa 2Ca 2Cu 3- yZn yO 10- δ ( y = 0, 2.65) superconductors have been performed and compared. These studies revealed that the charge state of thallium in the Cu 0.5Tl 0.5Ba 2O 4- δ charge reservoir layer in Zn doped samples is Tl 1+, while it is a mix of Tl 1+ and Tl 2+ in Zn free samples. The binding energy of Ba atoms in the Zn doped samples is shifted to higher energy, which when considered along with the presence of Tl 1+ suggested that it more efficiently directed the carriers to ZnO 2 and CuO 2 planes. The evidence of improved inter-plane coupling witnessed in X-ray diffraction is also confirmed by XPS measurements of Ca atoms in the Zn doped samples. The shift of the valance band spectrum in these Zn doped samples to higher energies suggested that the electrons at the top edge of the valance band were tied to a higher binding energy (relative to samples without Zn doping), which most likely resulted in a much lower energy state of the system in the superconducting state. The stronger superconducting state arising out of these effects is witnessed in the form of increased Tc( R = 0), Jc and the extent of diamagnetism in the final compound.

Modelling removal mechanisms of Pb, Cu, Zn and Cd in acidic groundwater during the neutralization by ambient surface and ground waters

USGS Publications Warehouse

Paulson, Anthony J.; Balistrieri, Laurie S.

1999-01-01

Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.

Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Weis, D. A.; Orians, K. J.

2010-12-01

In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd

Near room temperature and large-area synthesis of ZnO/Cu2O heterojunction for photocatalytic properties

NASA Astrophysics Data System (ADS)

Gao, Shiyong; Zhang, Jiejing; Li, Wenqiang; Jiao, Shujie; Nie, Yanguang; Fan, Huaiyun; Zeng, Zhi; Yu, Qingjiang; Wang, Jinzhong; Zhang, Xitian

2018-01-01

Large-area ZnO/Cu2O heterojunction have been successfully synthesized on Cu foil through a simple two-step solution method at near room temperature. The field emission scanning electron microscopy characterization indicates that the morphology of as-prepared Cu2O film grown on Cu foil is octahedral structure with diameter of ∼450 nm and ZnO is nanorod arrays structure with diameter of ∼150 nm. The current-voltage measurement of ZnO/Cu2O heterojunction shows a typical rectifying characteristics. Moreover, the photocatalytic test indicates that ZnO/Cu2O heterojunction exhibits high photocatalytic efficient for degradation of congo red dyes. The possible photocatalytic mechanism of ZnO/Cu2O heterojunction is also presented.

Erythrocyte CuZn superoxide dismutase activity is decreased in iron-deficiency anemia.

PubMed

Olivares, M; Araya, M; Pizarro, F; Letelier, A

2006-09-01

Iron and copper are essential microminerals that are intimately related. The present study was performed to determine the effect of iron-deficiency anemia (IDA) and treatment with iron on laboratory indicators of copper status. Hemoglobin, mean corpuscular volume erythrocyte Zn protoporphyrin, serum ferritin, serum copper, serum ceruloplasmin, and erythrocyte CuZn-superoxide dismutase (SOD) activity were studied in 12 adult women with IDA before and after iron treatment for 60-90 d (100 mg/d Fe, as ferric polymaltose) and in 27 women with normal iron status. Prior to treatment with iron, serum copper and ceruloplasmin were not different between the groups and treatment with iron did not affect these measures. IDA women, before and after treatment with iron, presented a 2.9- and 2-fold decrease in erythrocyte CuZn-SOD activity compared to women with normal iron status (p < 0.001). Treatment with iron increased erythrocyte CuZn-SOD activity of the IDA group; however, this change was not statistically significant. In conclusion, CuZn-SOD activity is decreased in IDA. Measurement of this enzyme activity is not useful for evaluating copper nutrition in iron-deficient subjects.

Germination, Physiological Responses and Gene Expression of Tall Fescue (Festuca arundinacea Schreb.) Growing under Pb and Cd

PubMed Central

Lou, Yanhong; Zhao, Peng; Wang, Deling; Amombo, Erick; Sun, Xin; Wang, Hui; Zhuge, Yuping

2017-01-01

Cadmium (Cd) and lead (Pb) are recognized as the most toxic metal ions due to their detrimental effects not only to plants, but also to humans. The objective of this study was to investigate the effects of Cd and Pb treatments on seed germination, plant growth, and physiological response in tall fescue (Festuca arundinacea Schreb.). We employed six treatments: CK (nutrient solution as control), T1 (1000 mg L-1 Pb), T2 (50 mg L-1 Cd), T3 (150 mg L-1 Cd), T4 (1000 mg L-1 Pb+50 mg L-1 Cd), T5 (1000 mg L-1 Pb+150 mg L-1 Cd). Antagonistic and synergistic actions were observed in tall fescue under Pb and Cd combined treatments. Under low Cd, plants exhibited higher relative germination rate, germ length, VSGR, catalase (CAT) and peroxidase (POD) activities. Additionally, in the shoots, the gene expression level of Cu/Zn SOD, FeSOD, POD, GPX, translocation factors, MDA, EL, and soluble protein contents were reduced under Pb stress. Conversely, under high Cd level, there was a decline in NRT, Pb content in shoots, Pb translocation factors, CAT activity; and an increase in VSGR, Pb content in roots, gene expression level of Cu/ZnSOD and POD in tall fescue exposed to Pb2+ regimes. On the other hand, tall fescue plants treated with low Cd exhibited lower relative germination rate, germination index, germ length, NRT, Cd content in roots. On the other hand there was higher Cd content, Cd translocation factor, CAT and POD activities, and gene expression level of Cu/Zn SOD, FeSOD, POD, GPX under Pb treatment compared with single Cd2+ treatment in the shoots. However, after high Cd exposure, plants displayed lower NRT, Cd content, CAT activity, and exhibited higher Cd contents, Cd translocation factor, MDA content, gene expression level of Cu/ZnSOD and GPX with the presence of Pb2+ relative to single Cd2+ treatment. These findings lead to a conclusion that the presence of low Cd level impacted positively towards tall fescue growth under Pb stress, while high level of Cd impacted

Germination, Physiological Responses and Gene Expression of Tall Fescue (Festuca arundinacea Schreb.) Growing under Pb and Cd.

PubMed

Lou, Yanhong; Zhao, Peng; Wang, Deling; Amombo, Erick; Sun, Xin; Wang, Hui; Zhuge, Yuping

2017-01-01

Cadmium (Cd) and lead (Pb) are recognized as the most toxic metal ions due to their detrimental effects not only to plants, but also to humans. The objective of this study was to investigate the effects of Cd and Pb treatments on seed germination, plant growth, and physiological response in tall fescue (Festuca arundinacea Schreb.). We employed six treatments: CK (nutrient solution as control), T1 (1000 mg L-1 Pb), T2 (50 mg L-1 Cd), T3 (150 mg L-1 Cd), T4 (1000 mg L-1 Pb+50 mg L-1 Cd), T5 (1000 mg L-1 Pb+150 mg L-1 Cd). Antagonistic and synergistic actions were observed in tall fescue under Pb and Cd combined treatments. Under low Cd, plants exhibited higher relative germination rate, germ length, VSGR, catalase (CAT) and peroxidase (POD) activities. Additionally, in the shoots, the gene expression level of Cu/Zn SOD, FeSOD, POD, GPX, translocation factors, MDA, EL, and soluble protein contents were reduced under Pb stress. Conversely, under high Cd level, there was a decline in NRT, Pb content in shoots, Pb translocation factors, CAT activity; and an increase in VSGR, Pb content in roots, gene expression level of Cu/ZnSOD and POD in tall fescue exposed to Pb2+ regimes. On the other hand, tall fescue plants treated with low Cd exhibited lower relative germination rate, germination index, germ length, NRT, Cd content in roots. On the other hand there was higher Cd content, Cd translocation factor, CAT and POD activities, and gene expression level of Cu/Zn SOD, FeSOD, POD, GPX under Pb treatment compared with single Cd2+ treatment in the shoots. However, after high Cd exposure, plants displayed lower NRT, Cd content, CAT activity, and exhibited higher Cd contents, Cd translocation factor, MDA content, gene expression level of Cu/ZnSOD and GPX with the presence of Pb2+ relative to single Cd2+ treatment. These findings lead to a conclusion that the presence of low Cd level impacted positively towards tall fescue growth under Pb stress, while high level of Cd impacted

Synergies between Unsaturated Zn/Cu Doping Sites in Carbon Dots Provide New Pathways for Photocatalytic Oxidation

DOE PAGES

Wu, Wenting; Zhang, Qinggang; Wang, Ruiqin; ...

2017-12-07

Unsaturated metal species (UMS) confined in nanomaterials play important roles for electron transfer in a wide range of catalytic reactions. However, the limited fabrication methods of UMS restrict their wider catalytic applications. Here in this paper, we report on the synergy of unsaturated Zn and Cu dopants confined in carbon dots (ZnCu-CDs) to produce enhanced electron transfer and photooxidation processes in the doped CDs. The Zn/Cu species chelate with the carbon matrix mainly through Cu-O(N)-Zn-O(N)-Cu complexes. Within this structure, Cu 2+ acts as a mild oxidizer that facilely increases the unsaturated Zn content and also precisely tunes the unsaturated Znmore » valence state to Zn d+, where d is between 1 and 2, instead of Zn. With the help of UMS, electron-transfer pathways are produced, enhancing both the electron donating (7.0 times) and-accepting (5.3 times) abilities relative to conventional CDs. Because of these synergistic effects, the photocatalytic efficiency of CDs in photooxidation reactions is shown to improve more than 5-fold.« less

Point defects in Cu 2 ZnSnSe 4 (CZTSe): Resonant X-ray diffraction study of the low-temperature order/disorder transition: Point defects in Cu 2 ZnSnSe 4 (CZTSe)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schelhas, L. T.; Stone, K. H.; Harvey, S. P.

The interest in Cu2ZnSn(S,Se)4 (CZTS) for photovoltaic applications is motivated by similarities to Cu(In,Ga)Se2 while being comprised of non-toxic and earth abundant elements. However, CZTS suffers from a Voc deficit, where the Voc is much lower than expected based on the band gap, which may be the result of a high concentration of point-defects in the CZTS lattice. Recently, reports have observed a low-temperature order/disorder transition by Raman and optical spectroscopies in CZTS films and is reported to describe the ordering of Cu and Zn atoms in the CZTS crystal structure. To directly determine the level of Cu/Zn ordering, wemore » have used resonant-XRD, a site, and element specific probe of long range order. We used CZTSe films annealed just below and quenched from just above the transition temperature; based on previous work, the Cu and Zn should be ordered and highly disordered, respectively. Our data show that there is some Cu/Zn ordering near the low temperature transition but significantly less than high chemical order expected from Raman. To understand both our resonant-XRD results and the Raman results, we present a structural model that involves antiphase domain boundaries and accommodates the excess Zn within the CZTS lattice.« less

Evidences for Cu and Zn Isotope Fractionation in Sediments and Particulate Suspended Matter of the Scheldt Estuary

NASA Astrophysics Data System (ADS)

Petit, J.; Mattielli, N.; de Jong, J.; Chou, L.

2004-05-01

Recent developments in MC-ICP-MS technology allow high precision measurements of heavy stable isotopes, such as Cu and Zn isotopes, which have been shown to undergo biotic or abiotic fractionation (1). Application of Zn isotopes to the study of aquatic ecosystems has already shown some interesting perspectives in their potential use as biogeochemical tracers in deep ocean carbonates (2) or Fe-Mn nodules (3). However, until now no investigation of possible Cu and Zn isotopic fractionation has been carried out within estuaries that are important pathways for hydrological and geochemical cycling of metals. Cu and Zn isotope geochemistry has been studied in sandy to loamy surface sediments (top 20 cm) and in suspended particulate matter (SPM) along a transect in a strong tidal estuary, the Scheldt estuary situated in Belgium and the Netherlands (November 2002). Further to separation of Cu, Fe and Zn by one step ion-exchange chromatography, Cu and Zn isotopic ratios are measured with a "Nu-Plasma" MC-ICP-MS. Instrumental mass bias is corrected using reference materials (Zn JMC, Cu NIST SRM 976 and Ga JMC standard) by simultaneous standard-sample bracketing and external normalization (500 ppb Zn doping for Cu isotopic analyses in static mode and 250 ppb Ga doping for Zn isotopic analyses in dynamic mode), together with a Ni correction. These methods lead to long-term reproducibility (2σ at 95 % confidence level) of ± 0.07 per mil for δ 66Zn (n=100 over 7 analysis sessions) and ± 0.06 per mil for δ 65Cu (n=120 over 8 analysis sessions) for 500 ppb of reference material. Average beam intensities are 6 V/ppm. Precise and reproducible results are obtained for concentration as low as 100 ppb for Cu and Zn. Expected Cu and Zn enrichment in SPM (120 ppm and 1200 ppm respectively) and sediments (being 6 to 10 times lower than SPM) in the upper estuary and progressive decrease in metal content by mixing downstream of the maximum turbidity zone (MTZ, around 5 psu) are

Facile synthesis of core-shell Cu2O@ ZnO structure with enhanced photocatalytic H2 production

NASA Astrophysics Data System (ADS)

Zhang, Yong-Hui; Jiu, Bei-Bei; Gong, Fei-Long; Lu, Kuan; Jiang, Nan; Zhang, Hao-Li; Chen, Jun-Li

2018-05-01

Core-shell Cu2O@ZnO composites were synthesized successfully based on a one-pot hydrothermal method in the presence of dioctyl sulfosuccinate sodium salt (AOT) surfactant. The Cu2O can be converted to rough core-shell Cu2O@ZnO structure by adjusting the amount of zinc powder added. The as-synthesized Cu2O@ZnO composites exhibited excellent photocatalytic activity and the amount of H2 generated using these composites was 4.5-fold more than that produced with Cu2O cubes. A possible photocatalytic mechanism for the Cu2O@ZnO composites with enhanced photocatalytic activity could be the separation by ZnO of the effective charge carriers.

The effect of intermetallic compound morphology on Cu diffusion in Sn-Ag and Sn-Pb solder bump on the Ni/Cu Under-bump metallization

NASA Astrophysics Data System (ADS)

Jang, Guh-Yaw; Duh, Jenq-Gong

2005-01-01

The eutectic Sn-Ag solder alloy is one of the candidates for the Pb-free solder, and Sn-Pb solder alloys are still widely used in today’s electronic packages. In this tudy, the interfacial reaction in the eutectic Sn-Ag and Sn-Pb solder joints was investigated with an assembly of a solder/Ni/Cu/Ti/Si3N4/Si multilayer structures. In the Sn-3.5Ag solder joints reflowed at 260°C, only the (Ni1-x,Cux)3Sn4 intermetallic compound (IMC) formed at the solder/Ni interface. For the Sn-37Pb solder reflowed at 225°C for one to ten cycles, only the (Ni1-x,Cux)3Sn4 IMC formed between the solder and the Ni/Cu under-bump metallization (UBM). Nevertheless, the (Cu1-y,Niy)6Sn5 IMC was observed in joints reflowed at 245°C after five cycles and at 265°C after three cycles. With the aid of microstructure evolution, quantitative analysis, and elemental distribution between the solder and Ni/Cu UBM, it was revealed that Cu content in the solder near the solder/IMC interface played an important role in the formation of the (Cu1-y,Niy)6Sn5 IMC. In addition, the diffusion behavior of Cu in eutectic Sn-Ag and Sn-Pb solders with the Ni/Cu UBM were probed and discussed. The atomic flux of Cu diffused through Ni was evaluated by detailed quantitative analysis in an electron probe microanalyzer (EPMA). During reflow, the atomic flux of Cu was on the order of 1016-1017 atoms/cm2sec in both the eutectic Sn-Ag and Sn-Pb systems.

Sediment-hosted Pb-Zn Deposits: a global perspective

USGS Publications Warehouse

Leach, David L.; Sangster, Donald F.; Kelley, Karen D.; Large, R; Garven, G.; Allen, Craig R.

2005-01-01

Sediment-hosted Pb-Zn deposits contain the world's greatest lead and zinc resources and dominate world production of these metals. They are a chverse group of ore deposits hosted by a wide variety of carbonate and siliciclastic roch that have no obviolls genetic association with igneous activity. A nmge of ore-fortl1ing processes in a vmiety of geologic and tectonic environments created these deposits over at least two billion years of Earth history. The metals were precipitated by basinal brines in synsedimentary and early diagenetic to low-grade metamorphic environments. The deposits display a broad range of relationships to enclosing host rocks that includes stratiform, strata-bound, and discordant ores. These ores are divided into two broad subt)1Jes: Mississippi Valley-type (MVT) and sedimentmy exhalative (SEDEX), Despite the "exhalative" component inherent in the term "SEDEX," in this manusclipt, direct evidence of an exhalite in the ore or alteration component is not essential for a deposit to be classified as SEDEX. The presence of laminated sulfides parallel to bedding is assumed to be permissive evidence for exhalative ores. The chstinction between some SEDEX and MVT depOSits can be quite subjective because some SEDEX ores replaced carbonate, whereas some MVT depOSits formed in an early diagenetic environment and display laminated ore textures. Geologic and resource information are presented for 248 depositS that provide a framework to describe ,mel compare these deposits. Nine of tlle 10 largest sediment-hosted Pb-Zn deposits are SEDEX, Of the deposits that contain at least 2.5 million metric tons (Mt), there are 35 SEDEX (excluding Broken Hill-type) deposits and 15 MVT (excluding Iris-type) deposits. Despite the skewed distribution of the deposit size, the two deposits types have an excellent correlation between total tonnage and tonnage of contained metal (Pb + Zn), with a fairly consistent ratio of about lO/l, regardless of the size of the deposit or

Optoelectronic properties of candidate photovoltaic Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nhalil, Hariharan; Han, Dan; Du, Mao-Hua

High temperature synthesis and optical band gaps are reported for three candidate photovoltaic earth-abundant Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 semiconductors. The reported synthesis method is found to be more advantageous for KAg 2SbS 4 compared to the literature reported synthesis utilizing supercritical ammonia as a reaction medium, which produces a mixture of chalcogenide products. Based on optical diffuse reflectance data, Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 have band gaps in the 1.6–1.8 eV range, and are shown to be stable in ambient air for a period of 6 weeks, making themmore » attractive candidates for solar cell applications. Density functional theory (DFT) calculations indicate indirect band gaps for Cu 2PbSiS 4 and KAg 2SbS 4, and a nearly direct band gap for Ag 2PbGeS 4 with the calculated difference between indirect and direct gaps of only 30 meV. The p-type semiconducting behavior of Cu 2PbSiS 4, Ag 2PbGeS 4 is also verified by the transport measurments. The 3D connectivity of the polyanionic networks in these compounds results in dispersive valence and conduction bands, which is especially noticeable for KAg 2SbS 4. This fact is in part attributed to the presence of formally pentavalent SbV in this compound leading to empty Sb 5s orbitals in the conduction band. Finally, we discuss the potential of Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 for photovoltaic applications based on synthesis, stability, band gap and electronic structure considerations.« less

Optoelectronic properties of candidate photovoltaic Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 semiconductors

DOE PAGES

Nhalil, Hariharan; Han, Dan; Du, Mao-Hua; ...

2018-03-01

High temperature synthesis and optical band gaps are reported for three candidate photovoltaic earth-abundant Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 semiconductors. The reported synthesis method is found to be more advantageous for KAg 2SbS 4 compared to the literature reported synthesis utilizing supercritical ammonia as a reaction medium, which produces a mixture of chalcogenide products. Based on optical diffuse reflectance data, Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 have band gaps in the 1.6–1.8 eV range, and are shown to be stable in ambient air for a period of 6 weeks, making themmore » attractive candidates for solar cell applications. Density functional theory (DFT) calculations indicate indirect band gaps for Cu 2PbSiS 4 and KAg 2SbS 4, and a nearly direct band gap for Ag 2PbGeS 4 with the calculated difference between indirect and direct gaps of only 30 meV. The p-type semiconducting behavior of Cu 2PbSiS 4, Ag 2PbGeS 4 is also verified by the transport measurments. The 3D connectivity of the polyanionic networks in these compounds results in dispersive valence and conduction bands, which is especially noticeable for KAg 2SbS 4. This fact is in part attributed to the presence of formally pentavalent SbV in this compound leading to empty Sb 5s orbitals in the conduction band. Finally, we discuss the potential of Cu 2PbSiS 4, Ag 2PbGeS 4 and KAg 2SbS 4 for photovoltaic applications based on synthesis, stability, band gap and electronic structure considerations.« less

Biosorption of Pb2+ and Cu2+ in aqueous solutions using agricultural wastes

NASA Astrophysics Data System (ADS)

Nieva, Aileen D.; Doma, Bonifacio T.; Chao, Huan-Ping; Siang Leng, Lai

2017-11-01

This study aimed to determine and compare the adsorptive capacity of Pb2+ and Cu2+ in simulated wastewater onto three agricultural wastes The adsorption capacities of Pb2+ onto the agricultural wastes can be arranged as Litchi chinensis (4.30 mg of sorbate per g of sorbent (mg g-1), 85.68% adsorption) > Bambusa vulgaris (3.83 mg g-1, 76.19% adsorption) > Annona squamosa (2.70 mg g-1, 53.66% adsorption) while the adsorption capacities of Cu2+ onto the same agricultural wastes can be arranged in the order: Bambusa vulgaris (3.86 mg g-1, 77.17% adsorption) > Annona squamosal (3.58 mg g-1, 71.58% adsorption) > Litchi chinensis (3.42 mg g-1, 68.32% adsorption). The biosorbents had relatively higher adsorptive capacities with Cu2+ as compared to that of Pb2+ except for Litchi chinensis. Although the results show lower adsorptive capacity as compared to a number of treated agricultural wastes showing 80% up to almost 100% adsorption of Pb2+ and Cu2+, the results show that Annona squamosa, Bamubusa vulgaris, and Litchi chinensis are potential biosorbents and promote sustainable treatment process.

The determination of extinction coefficient of CuInS2, and ZnCuInS3 multinary nanocrystals.

PubMed

Qin, Lei; Li, Dongze; Zhang, Zhuolei; Wang, Kefei; Ding, Hong; Xie, Renguo; Yang, Wensheng

2012-10-21

A pioneering work for determining the extinction coefficient of colloidal semiconductor nanocrystals (NCs) has been cited over 1500 times (W. Yu, W. Guo, X. G. Peng, Chem. Mater., 2003, 15, 2854-2860), indicating the importance of calculating NC concentration for further research and applications. In this study, the size-dependent nature of the molar extinction coefficient of "greener" CuInS(2) and ZnCuInS(3) NCs with emission covering the whole visible to near infrared (NIR) is presented. With the increase of NC size, the resulting quantitative values of the extinction coefficients of ternary CuInS(2) and quaternary ZnCuInS(3) NCs are found to follow a power function with exponents of 2.1 and 2.5, respectively. Obviously, a larger value of extinction coefficient is observed in quaternary NCs for the same size of particles. The difference of the extinction coefficient from both samples is clearly demonstrated due to incorporating ZnS with a much larger extinction coefficient into CuInS(2) NCs.

The mutual influence of speciation and combination of Cu and Pb on the photodegradation of dimethyl o-phthalate.

PubMed

Jiang, Xinshu; Wang, Zhe; Zhang, Yiyue; Wang, Fei; Zhu, Mijia; Yao, Jun

2016-12-01

Specific industrial application of dimethyl o-phthalate (DMP) in ore flotation has led to DMP-heavy metals combined pollution, which causes the abiotic degradation of DMP in the environment more complex. This study focused on the effect of Cu and Pb on photodegradation of DMP. The major mechanism of inhibiting effect of Cu and Pb on degradation of DMP involved their speciation and combination. It was found that the Cu (5 mg/L, I = 95.4%) and Pb (5 mg/L, I = 100%) could inhibit the photodegradation of DMP. The main species that inhibit the DMP degradation were Cu(OH) + and Pb(OH) + , respectively. The intensity of the UV-Vis absorbance of DMP was obviously related to the concentration of Cu 2+ (R 2  = 0.8655) or Pb 2+ (R 2  = 0.9019) ions. Fluorescence quenching effect of Cu 2+ (R 2  > 0.9946), Pb 2+ (R 2  > 0.6879) on DMP is strongly correlated with the concentration of ions. And the equilibrium membrane dialysis experiment has also verified the combination of DMP and Cu, Pb. These results are useful to understand the effect mechanism of metal species on the photodegradation of organic chemicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cu-doped ZnO nanorod arrays: the effects of copper precursor and concentration

PubMed Central

2014-01-01

Cu-doped ZnO nanorods have been grown at 90°C for 90 min onto a quartz substrate pre-coated with a ZnO seed layer using a hydrothermal method. The influence of copper (Cu) precursor and concentration on the structural, morphological, and optical properties of ZnO nanorods was investigated. X-ray diffraction analysis revealed that the nanorods grown are highly crystalline with a hexagonal wurtzite crystal structure grown along the c-axis. The lattice strain is found to be compressive for all samples, where a minimum compressive strain of −0.114% was obtained when 1 at.% Cu was added from Cu(NO3)2. Scanning electron microscopy was used to investigate morphologies and the diameters of the grown nanorods. The morphological properties of the Cu-doped ZnO nanorods were influenced significantly by the presence of Cu impurities. Near-band edge (NBE) and a broad blue-green emission bands at around 378 and 545 nm, respectively, were observed in the photoluminescence spectra for all samples. The transmittance characteristics showed a slight increase in the visible range, where the total transmittance increased from approximately 80% for the nanorods doped with Cu(CH3COO)2 to approximately 90% for the nanorods that were doped with Cu(NO3)2. PMID:24855460

Phytotoxic effects of Cu and Zn on soybeans grown in field-aged soils: their additive and interactive actions.

PubMed

Kim, Bojeong; McBride, Murray B

2009-01-01

A field pot experiment was conducted to investigate the interactive phytotoxicity of soil Cu and Zn on soybean plants [Glycine max (L.) Merr.]. Two soils (Arkport sandy loam [coarse-loamy, mixed, active, mesic Lamellic Hapludalf] and Hudson silty clay loam [fine, illitic, mesic Glossaquic Hapludalf]) spiked with Cu, Zn, and combinations of both to reach the final soil metal range of 0 to 400 mg kg(-1) were tested in a 2-yr bioassay after 1 yr of soil-metal equilibration in the field. The soluble and easily-extractable fraction of soil Zn (or Cu), estimated by dilute CaCl2, increased linearly in response to the total Zn (or Cu) added. This linearity was, however, strongly affected where soils were treated with both metals in combination, most notably for Zn, as approximately 50% more of soil Zn was extracted into solution when the Cu level was high. Consequently, added Zn is less likely to be stabilized by aging than added Cu when both metals are present in field soils. The predictive model relating soil metal extractability to plant Zn concentration also revealed a significant Cu-Zn interaction. By contrast, the interaction between the two metals contributed little to explain plant Cu uptake. The additive action of soil Cu and Zn was of considerable importance in explaining plant biomass reduction. This work clearly demonstrates the critical roles of the properties of the soil, the nature of the metal, and the level of other toxic metals present on the development of differential phytotoxicity due to soil Cu and Zn.

Effect of Cu2+ substitution on the magnetic properties of co-precipitated Ni-Cu-Zn ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ramakrishna, K. S.; Srinivas, Ch.; Tirupanyam, B. V.; Ramesh, P. N.; Meena, S. S.; Potukuchi, D. M.; Sastry, D. L.

2017-05-01

Spinel ferrite nanoparticles with chemical equation NixCu0.1Zn0.9-xFe2O4 (x = 0.5, 0.6, 0.7) have been synthsized using co-precipitation method followed by heat treatment at a temperature of 200 °C for 2h. The results of XRD, FE-SEM and VSM studies are reported. XRD patterns confirm the formation of cubic spinel phase of ferrite samples along with small amount of a secondary phase of α-Fe2O3 whose concentration decreases as Ni2+ concentration increases. The crystallite sizes (in the range of 7.5-13.9 nm) increase and the lattice parameter decreases with increase in Ni2+ ion concentration. These values are comparable to those of NiZn ferrite without Cu substitution. It has been observed that there is a considerable reduction in saturation magnetisation (Ms). This and differences in other magnetic parameters are attributed to considerable changes in cation distribution or core shell interactions of NiZn ferrite with 10 mole% Cu substitution in the place of Zn.

Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Nakamura, Junji; Fujitani, Tadahiro; Kuld, Sebastian; Helveg, Stig; Chorkendorff, Ib; Sehested, Jens

2017-09-01

Kattel et al (Reports, 24 March 2017, p. 1296) report that a zinc on copper (Zn/Cu) surface undergoes oxidation to zinc oxide/copper (ZnO/Cu) during carbon dioxide (CO 2 ) hydrogenation to methanol and conclude that the Cu-ZnO interface is the active site for methanol synthesis. Similar experiments conducted two decades ago by Fujitani and Nakamura et al demonstrated that Zn is attached to formate rather than being fully oxidized. Copyright © 2017, American Association for the Advancement of Science.

Pb-free Sn-Ag-Cu ternary eutectic solder

DOEpatents

Anderson, Iver E.; Yost, Frederick G.; Smith, John F.; Miller, Chad M.; Terpstra, Robert L.

1996-06-18

A Pb-free solder includes a ternary eutectic composition consisting essentially of about 93.6 weight % Sn-about 4.7 weight % Ag-about 1.7 weight % Cu having a eutectic melting temperature of about 217.degree. C. and variants of the ternary composition wherein the relative concentrations of Sn, Ag, and Cu deviate from the ternary eutectic composition to provide a controlled melting temperature range (liquid-solid "mushy" zone) relative to the eutectic melting temperature (e.g. up to 15.degree. C. above the eutectic melting temperature).

Pb-free Sn-Ag-Cu ternary eutectic solder

DOEpatents

Anderson, I.E.; Yost, F.G.; Smith, J.F.; Miller, C.M.; Terpstra, R.L.

1996-06-18

A Pb-free solder includes a ternary eutectic composition consisting essentially of about 93.6 weight % Sn-about 4.7 weight % Ag-about 1.7 weight % Cu having a eutectic melting temperature of about 217 C and variants of the ternary composition wherein the relative concentrations of Sn, Ag, and Cu deviate from the ternary eutectic composition to provide a controlled melting temperature range (liquid-solid ``mushy`` zone) relative to the eutectic melting temperature (e.g. up to 15 C above the eutectic melting temperature). 5 figs.

Microstructural Evolution and Tensile Properties of SnAgCu Mixed with Sn-Pb Solder Alloys (Preprint)

DTIC Science & Technology

2009-03-01

AFRL-RX-WP-TP-2009-4132 MICROSTRUCTURAL EVOLUTION AND TENSILE PROPERTIES OF SnAgCu MIXED WITH Sn-Pb SOLDER ALLOYS (PREPRINT...PROPERTIES OF SnAgCu MIXED WITH Sn-Pb SOLDER ALLOYS (PREPRINT) 5a. CONTRACT NUMBER FA8650-04-C-5704 5b. GRANT NUMBER 5c. PROGRAM ELEMENT...ANSI Std. Z39-18 Microstructural evolution and tensile properties of SnAgCu mixed with Sn-Pb solder alloys Fengjiang Wang,1 Matthew O’Keefe,1,2 and

Effects of Zn²⁺ and Cu²⁺ on loach ovaries and ova development.

PubMed

Tang, Jian-Xun; Li, Jun-Rong; Liu, Zhong-Liang; Zhao, Hua; Tao, Xiao-Min; Cheng, Zhang-Shun

2013-10-01

This study compared the accumulation of Zn²⁺ and Cu²⁺ in the ovaries and ova of loaches under different concentrations of Zn²⁺ (1.00, 2.50 and 5.00 mg/L respectively) and Cu²⁺ (0.10, 0.25 and 0.50 mg/L respectively). The results showed that both Zn²⁺ and Cu²⁺ accumulated in the ovaries, and that the relationship between accumulation and time was linear over 20 days of exposure. The accumulation of the metals in ovaries was closely related to the concentration of exposure in the solutions (P<0.05), and was obviously affected by the time and doses. However, the Cu²⁺ concentration was significantly higher than Zn²⁺ (P<0.05). The development level of ova in the ovaries also correlated with the concentration and exposure period in the Zn²⁺ and Cu²⁺ solutions. This study compared the accumulation of Zn 2+ and Cu 2+ in the ovaries and ova of loaches under different concentrations of Zn 2+ (1.00, 2.50 and 5.00 mg/L respectively) and Cu 2+ (0.10, 0.25 and 0.50 mg/L respectively). The results showed that both Zn 2+ and Cu 2+ accumulated in the ovaries, and that the relationship between accumulation and time was linear over 20 days of exposure. The accumulation of the metals in ovaries was closely related to the concentration of exposure in the solutions ( P< 0.05), and was obviously affected by the time and doses. However, the Cu 2+ concentration was significantly higher than Zn 2+ ( P< 0.05). The development level of ova in the ovaries also correlated with the concentration and exposure period in the Zn 2+ and Cu 2+ solutions.

Synthesis and photoelectrochemical properties of a novel CuO/ZnO nanorod photocathode for solar hydrogen generation

NASA Astrophysics Data System (ADS)

Shaislamov, Ulugbek; Lee, Heon-Ju

2016-10-01

Here, we present a facile synthesis method and photoelectrochemical characterizations of a p-type CuO-nanorod array photoelectrode with ZnO nanorod branches. Vertically-aligned CuO nanorods were synthesized by using direct oxidation of metallic Cu nanorods grown on a Cu substrate by using a facile template-assisted electrodeposition method. The formed CuONR/ZnONB hierarchically-structured photoelectrode exhibited remarkable photoelectrodechemical performance and outstanding stability compared to the CuO NR photoelectrode without ZnO NR branches. Morphological, optical and electrochemical characterizations were carried out in order to examine the effects of ZnO nanorod branches on the stability and the overall electrochemical performance of the electrode.

Constitutive Behavior of Mixed Sn-Pb/Sn-3.0Ag-0.5Cu Solder Alloys

NASA Astrophysics Data System (ADS)

Tucker, J. P.; Chan, D. K.; Subbarayan, G.; Handwerker, C. A.

2012-03-01

During the transition from Pb-containing solders to Pb-free solders, joints composed of a mixture of Sn-Pb and Sn-Ag-Cu often result from either mixed assemblies or rework. Comprehensive characterization of the mechanical behavior of these mixed solder alloys resulting in a deformationally complete constitutive description is necessary to predict failure of mixed alloy solder joints. Three alloys with 1 wt.%, 5 wt.%, and 20 wt.% Pb were selected so as to represent reasonable ranges of Pb contamination expected from different 63Sn-37Pb components mixed with Sn-3.0Ag-0.5Cu. Creep and displacement-controlled tests were performed on specially designed assemblies at temperatures of 25°C, 75°C, and 125°C using a double lap shear test setup that ensures a nearly homogeneous state of plastic strain at the joint interface. The observed changes in creep and tensile behavior with Pb additions were related to phase equilibria and microstructure differences observed through differential scanning calorimetric and scanning electron microscopic cross-sectional analysis. As Pb content increased, the steady-state creep strain rates increased, and primary creep decreased. Even 1 wt.% Pb addition was sufficient to induce substantially large creep strains relative to the Sn-3.0Ag-0.5Cu alloy. We describe rate-dependent constitutive models for Pb-contaminated Sn-Ag-Cu solder alloys, ranging from the traditional time-hardening creep model to the viscoplastic Anand model. We illustrate the utility of these constitutive models by examining the inelastic response of a chip-scale package (CSP) under thermomechanical loading through finite-element analysis. The models predict that, as Pb content increases, total inelastic dissipation decreases.

ZnO nanoflower-based photoelectrochemical DNAzyme sensor for the detection of Pb2+.

PubMed

Zhang, Bintian; Lu, Lili; Hu, Qichang; Huang, Feng; Lin, Zhang

2014-06-15

Lead contamination is now widespread, and exposure to lead may cause adverse effects on human beings. In this study, a photoelectrochemical sensor based on flower-like ZnO nanostructures was developed for Pb(2+) detection, using a Pb(2+)-dependent DNAzyme as the recognition unit and a double-strand DNA intercalator, Ru(bpy)2(dppz)(2+) (bpy=2,2'-bipyridine, dppz=dipyrido[3,2-a:2',3'-c] phenazine) as the photoelectrochemical signal reporter. The ZnO nanoflower was fabricated on an indium tin oxide (ITO) electrode by the convenient hydrothermal decomposition method. The morphology and photoelectrochemical property of the ZnO nanoflowers were characterized by SEM, XRD and photocurrent measurements. DNAzyme-substrate duplex was assembled on an ITO/ZnO electrode through electrostatic adsorption. In the presence of Pb(2+), RNA-cleavage activity of the DNAzyme was activated and its substrate strand was cleaved, resulting in the release of Ru(bpy)2(dppz)(2+) from the DNA film and the concomitant photocurrent decrease. The detection principle was verified by fluorescence measurements. Under the optimized conditions, a linear relationship between photocurrent and Pb(2+) concentration was obtained over the range of 0.5-20 nM, with a detection limit of 0.1 nM. Interference from other common metal ions was found negligible. Applicability of the sensor was demonstrated by analyzing lead level in human serum and Pb(2+) spiked water samples. This facile and economical sensor system showed high sensitivity and selectivity, thus can be potentially applied for on-site monitoring of lead contaminant. Copyright © 2014 Elsevier B.V. All rights reserved.

Mobility of Heavy Metals (Pb, Cd, Zn) in the Pampeano and Puelche Aquifers, Argentina: Partition and Retardation Coefficients.

PubMed

Jakomin, L M; Marbán, L; Grondona, S; Glok Galli, M; Martínez, D E

2015-09-01

The prediction about metals behaviour in soil requires knowledge on their solid-liquid partitioning. Usually it is expressed with an empirical distribution coefficient or Kd, which gives the ratio of the metal concentration in the solid phase to that in the solution. Kd values have been determined for Zn, Pb and Cd from samples representing the two most exploited aquifers in Argentina, Pampeano and Puelche, at three different locations in the province of Buenos Aires. The Pampeano aquifer presented higher Kd values than the Puelche aquifer. Comparing Kd values, different relationships could be observed: (a) Pampeano aquifer: Pb > Zn > Cd, and (b) Puelche aquifer: Pb > Cd > Zn. Kd for Cd seems to be linked to cationic exchange capacity, but solid phases precipitation can be more determining for Pb and Zn.

Molecular cloning and characterization of Siamese crocodile (Crocodylus siamensis) copper, zinc superoxide dismutase (CSI-Cu,Zn-SOD) gene.

PubMed

Sujiwattanarat, Penporn; Pongsanarakul, Parinya; Temsiripong, Yosapong; Temsiripong, Theeranan; Thawornkuno, Charin; Uno, Yoshinobu; Unajak, Sasimanas; Matsuda, Yoichi; Choowongkomon, Kiattawee; Srikulnath, Kornsorn

2016-01-01

Superoxide dismutase (SOD, EC 1.15.1.1) is an antioxidant enzyme found in all living cells. It regulates oxidative stress by breaking down superoxide radicals to oxygen and hydrogen peroxide. A gene coding for Cu,Zn-SOD was cloned and characterized from Siamese crocodile (Crocodylus siamensis; CSI). The full-length expressed sequence tag (EST) of this Cu,Zn-SOD gene (designated as CSI-Cu,Zn-SOD) contained 462bp encoding a protein of 154 amino acids without signal peptides, indicated as intracellular CSI-Cu,Zn-SOD. This agreed with the results from the phylogenetic tree, which indicated that CSI-Cu,Zn-SOD belonged to the intracellular Cu,Zn-SOD. Chromosomal location determined that the CSI-Cu,Zn-SOD was localized to the proximal region of the Siamese crocodile chromosome 1p. Several highly conserved motifs, two conserved signature sequences (GFHVHEFGDNT and GNAGGRLACGVI), and conserved amino acid residues for binding copper and zinc (His(47), His(49), His(64), His(72), His(81), Asp(84), and His(120)) were also identified in CSI-Cu,Zn-SOD. Real-time PCR analysis showed that CSI-Cu,Zn-SOD mRNA was expressed in all the tissues examined (liver, pancreas, lung, kidney, heart, and whole blood), which suggests a constitutively expressed gene in these tissues. Expression of the gene in Escherichia coli cells followed by purification yielded a recombinant CSI-Cu,Zn-SOD, with Km and Vmax values of 6.075mM xanthine and 1.4×10(-3)mmolmin(-1)mg(-1), respectively. This Vmax value was 40 times lower than native Cu,Zn-SOD (56×10(-3)mmolmin(-1)mg(-1)), extracted from crocodile erythrocytes. This suggests that cofactors, protein folding properties, or post-translational modifications were lost during the protein purification process, leading to a reduction in the rate of enzyme activity in bacterial expression of CSI-Cu,Zn-SOD. Copyright © 2015 Elsevier Inc. All rights reserved.

Antifriction coating of Cu-Fe-Al-Pb system for plain bearings

NASA Astrophysics Data System (ADS)

Kotenkov, Pavel; Kontsevoi, Yurii; Mejlakh, Anna; Pastukhov, Eduard; Shubin, Alexey; Goyda, Eduard; Sipatov, Ivan

2017-09-01

Aluminium, copper and their compounds are used in common as basis for antifriction coatings of plain bearings. Antifriction testing of plain bearings (based on Al and Cu) made by leading automotive manufacturers from Germany, Japan, USA, United Kingdom and Russia were carried out to make judicious selection of basis for development of new antifriction material. Testing was carried out using friction machine. It was defined that materials based on Cu provide better durability and robustness of plain bearings in comparison with Al based ones. The new antifriction composite coatings based on copper were developed taking into account the requirements specified for plain bearings of internal-combustion engine. Pilot samples of plain bearings with antifriction coatings of Cu-Fe-Al-Pb system were produced. The antifriction composite having Cu-5Fe-5Al5Fe2-10Pb (mass %) composition has demonstrated low friction factor and high wear-resistance. Metallographic analysis of pilot samples was carried out by means of optical and scanning electron microscopy.

Tolerance and biosorption of copper (Cu) and lead (Pb) by filamentous fungi isolated from a freshwater ecosystem.

PubMed

Iskandar, Nur Liyana; Zainudin, Nur Ain Izzati Mohd; Tan, Soon Guan

2011-01-01

Filamentous fungi are able to accumulate significant amount of metals from their environment. The potential of fungal biomass as agents for biosorption of heavy metals from contaminated sediments is currently receiving attention. In the present study, a total of 41 isolates of filamentous fungi obtained from the sediment of the Langat River, Selangor, Malaysia were screened for their tolerance and uptake capability of copper (Cu) and lead (Pb). The isolates were identified as Aspergillus niger, A. fumigatus, Trichoderma asperellum, Penicillium simplicissimum and P. janthinellum. A. niger and P. simplicissimum, were able to survive at 1000 mg/L of Cu(II) concentration on Potato Dextrose Agar (PDA) while for Pb, only A. niger survived at 5000 mg/L concentration. The results showed that A. niger, P. simplicissimum and T. asperellum have a better uptake capacity for Pb compared to Cu and the findings indicated promising biosorption of Cu and Pb by these filamentous fungi from aqueous solution. The present study was also determined the maximum removal of Cu(II) and Pb(II) that was performed by A. niger. The metal removal which occurred at Cu(II) 200 mg/L was (20.910 +/- 0.581) mg/g and at 250 mg/L of Pb(II) was (54.046 +/- 0.328) mg/g.

Phytoextraction of Zn and Cu from sewage sludge and impact on agronomic characteristics.

PubMed

Xiaomei, Liu; Qitang, Wu; Banks, M K; Ebbs, S D

2005-01-01

The presence of elevated concentrations of heavy metals limits the usage of sewage sludge as a fertilizer and soil amendment. Experiments were carried out to examine the extent to which seven plant species phytoextracted Zn and Cu from dewatered sludge. The hyperaccumulators Thlaspi caerulescens and Sedum alfredii showed the greatest removal of Zn, while shoots and tubers of two species of Alocasia showed the greatest Cu removal. Cultivation of plants in the sludge resulted in significant decreases in total Zn and changes in the partitioning of Zn between soil pools. However, Cu levels were largely unchanged and remained associated predominantly with the organic matter pool. Agronomic characteristics of the sludge material, such as pH, organic matter content, and nitrogen, phosphorus, and potassium concentrations, did not change significantly during the four-month growth period, indicating that subsequent crops could be sustained by this material. These results suggest that Zn can be phytoextracted from sludge material, provided the rate of metal uptake exceeds the rate of mobilization to the exchangeable fraction. Since there was no appreciable accumulation of Zn and Cu in seeds of Zea mays in this study, some tissues from sludge-grown plants could potentially be used as animal fodder.

Synthesis and characterization of Ce, Cu co-doped ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Harish, G. S.; Sreedhara Reddy, P.

2015-09-01

Ce, Cu co-doped ZnS nanoparticles were prepared at room temperature using a chemical co-precipitation method. The prepared nanoparticles were characterized by X- ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive analysis of X-rays (EDAX), diffuse reflectance spectroscopy (DRS), photoluminescence (PL) and high resolution Raman spectroscopic techniques. Transmission electron microscopy (TEM) and X-ray diffraction studies showed that the diameter of the particles was around 2-3 nm. Broadened XRD peaks revealed the formation of nanoparticles with a face centered cubic (fcc) structure. DRS studies confirmed that the band gap increased with an increase in the dopant concentration. The Raman spectra of undoped and Ce, Cu ions co-doped ZnS nanoparticles showed longitudinal optical mode and transverse optical mode. Compared with the Raman modes (276 and 351 cm-1) of undoped ZnS nanoparticles, the Raman modes of Ce, Cu co- doped ZnS nanoparticles were slightly shifted towards lower frequency. PL spectra of the samples showed remarkable enhancement in the intensity upon doping.

Reduced anti-ferromagnetism promoted by Zn 3d 10 substitution at CuO 2 planar sites of Cu 0.5Tl 0.5Ba 2Ca 3Cu 4O 12-δ superconductors

NASA Astrophysics Data System (ADS)

Mumtaz, M.; Khan, Nawazish A.

2009-11-01

The role of charge carriers in ZnO 2/CuO 2 planes of Cu 0.5Tl 0.5Ba 2Ca 3Cu 4-yZn yO 12-δ material in bringing about superconductivity has been explained. Due to suppression of anti-ferromagnetic order with Zn 3d 10 ( S=0) substitution at Cu 3d 9(S={1}/{2}) sites in the inner CuO 2 planes of Cu 0.5Tl 0.5Ba 2Ca 3Cu 4O 12-δ superconductor, the distribution of charge carriers becomes homogeneous and optimum, which is evident from the enhanced superconductivity parameters. The decreased c-axis length with the increase of Zn doping improves interlayer coupling and hence the three dimensional (3D) conductivity in the unit cell is enhanced. Also the softening of phonon modes with the increased Zn doping indicates that the electron-phonon interaction has an essential role in the mechanism of high- Tc superconductivity in these compounds.

Immobilization of Pb and Cu in polluted soil by superphosphate, multi-walled carbon nanotube, rice straw and its derived biochar.

PubMed

Rizwan, Muhammad Shahid; Imtiaz, Muhammad; Huang, Guoyong; Chhajro, Muhammad Afzal; Liu, Yonghong; Fu, Qingling; Zhu, Jun; Ashraf, Muhammad; Zafar, Mohsin; Bashir, Saqib; Hu, Hongqing

2016-08-01

Lead (Pb) and copper (Cu) contamination in croplands pose severe health hazards and environmental concerns throughout soil-food chain transfer. In the present study, BCR, TCLP, CaCl2, and SBET techniques were employed to evaluate the simultaneous effectiveness of rice straw (RS) and its derived biochar (BC), multiwall carbon nanotube (MWCNT), and single superphosphate (SSP) to immobilize the Pb and Cu in co-contaminated soil. The BCR sequential extraction results suggested that with increasing BC and SSP amount, the acid-soluble fractions decreased while oxidizable and residual proportions of Pb and Cu were increased significantly. Compared to SSP, the application of BC amendment substantially modified partitioning of Cu from easily exchangeable phase to less bioavailable residual bound fraction. The immobilized Pb and Cu were mainly transformed to reducible forms. The TCLP and CaCl2-extracted Pb and Cu were reduced significantly by the addition of BC compared to RS and MWCNT, whereas the bio-accessibility of Pb significantly reduced with RS addition. SSP showed better results for Pb immobilization while marginal for Cu in co-contaminated soil. Overall, the addition of BC offered the best results and could be effective in both Pb and Cu immobilization thereby reducing their mobility and bioavailability in the co-contaminated soil.

Low-temperature thermoelectric properties of Pb doped Cu2SnSe3

NASA Astrophysics Data System (ADS)

Prasad K, Shyam; Rao, Ashok; Gahtori, Bhasker; Bathula, Sivaiah; Dhar, Ajay; Chang, Chia-Chi; Kuo, Yung-Kang

2017-09-01

A series of Cu2Sn1-xPbxSe3 (0 ≤ x ≤ 0.04) compounds was prepared by solid state synthesis technique. The electrical resistivity (ρ) decreased with increase in Pb content up to x = 0.01, thereafter it increased with further increase in x (till x = 0.03). However, the lowest value of electrical resistivity is observed for Cu2Sn0.96Pb0.04Se3. Analysis of electrical resistivity of all the samples suggests that small poloron hoping model is operative in the high temperature regime while variable range hopping is effective in the low temperature regime. The positive Seebeck coefficient (S) for pristine and doped samples in the entire temperature range indicates that the majority charge carriers are holes. The electronic thermal conductivity (κe) of the Cu2Sn1-xPbxSe3 compounds was estimated by the Wiedemann-Franz law and found that the contribution from κe is less than 1% of the total thermal conductivity (κ). The highest ZT 0.013 was achieved at 400 K for the sample Cu2Sn0.98Pb0.02Se3, about 30% enhancement as compared to the pristine sample.

Electrochemically synthesis and optoelectronic properties of Pb- and Zn-doped nanostructured SnSe films

NASA Astrophysics Data System (ADS)

Jamali-Sheini, Farid; Cheraghizade, Mohsen; Yousefi, Ramin

2018-06-01

In this study, electrodeposition technique was applied to deposit un-, lead (Pb), and zinc (Zn)-doped SnSe films. X-ray diffraction (XRD) patterns of the films showed a polycrystalline SnSe phase with orthorhombic crystalline lattice. SEM images revealed ball-shaped, rod-shaped, and wire-shaped morphologies for SnSe films. Moreover, optical measurements indicated incorporation of dopant in the crystalline lattice of films by varying the optical energy band gap. Electrical characterization of Pb- and Zn-doped SnSe films showed their p-type nature. Finally, the solar cell device fabricated using the Zn-doped SnSe films reveal a higher efficiency because of their higher carrier concentration.

64Cu, a powerful positron emitter for immunoimaging and theranostic: Production via natZnO and natZnO-NPs.

PubMed

Karimi, Zahra; Sadeghi, Mahdi; Mataji-Kojouri, Naimeddin

2018-07-01

64 Cu is one of the most beneficial radionuclide that can be used as a theranostic agent in Positron Emission Tomography (PET) imaging. In this current work, 64 Cu was produced with zinc oxide nanoparticles ( nat ZnONPs) and zinc oxide powder ( nat ZnO) via the 64 Zn(n,p) 64 Cu reaction in Tehran Research Reactor (TRR) and the activity values were compared with each other. The theoretical activity of 64 Cu also was calculated with MCNPX-2.6 and the cross sections of this reaction were calculated by using TALYS-1.8, EMPIRE-3.2.2 and ALICE/ASH nuclear codes and were compared with experimental values. Transmission Electronic Microscopy (TEM), Scanning Electronic Microscopy (SEM) and X-Ray Diffraction (XRD) analysis were used for samples characterizations. From these results, it's concluded that 64 Cu activity value with nanoscale target was achieved more than the bulk state target and had a good adaptation with the MCNPX result. Copyright © 2018 Elsevier Ltd. All rights reserved.

Investigations on structural, vibrational and dielectric properties of nanosized Cu doped Mg-Zn ferrites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Anand; Department of Physics, MEDICAPS Institute of Science and Technology, Pithampur 453331; Rajpoot, Rambabu

2016-05-23

Transition metal Cu{sup 2+} doped Mg-Zn ferrite [Mg{sub 0.5}Zn{sub 0.5-x}Cu{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5)] were prepared by sol gel auto combustion (SGAC) method to probe the structural, vibrational and electrical properties. X-ray diffraction (XRD) pattern reveals a single-phase cubic spinel structure without the presence of any secondary phase corresponding to other structure. The average particle size of the parent Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} is found to be ~29.8 nm and is found to increase with Cu{sup 2+} doping. Progressive reduction in lattice parameter of Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} has been observed due to difference inmore » ionic radii of cations with improved Cu doping. Spinel cubic structure is further confirmed by Raman spectroscopy. Small shift in Raman modes towards higher wave number has been observed in doped Mg-Zn ferrites. The permittivity and dielectric loss decreases at lower doping and increases at higher order doping of Cu{sup 2+}.« less

Accumulation of lead (Pb) in brown trout (Salmo trutta) from a lake downstream a former shooting range.

PubMed

Mariussen, Espen; Heier, Lene Sørlie; Teien, Hans Christian; Pettersen, Marit Nandrup; Holth, Tor Fredrik; Salbu, Brit; Rosseland, Bjørn Olav

2017-01-01

An environmental survey was performed in Lake Kyrtjønn, a small lake within an abandoned shooting range in the south of Norway. In Lake Kyrtjønn the total water concentrations of Pb (14µg/L), Cu (6.1µg/L) and Sb (1.3µg/L) were elevated compared to the nearby reference Lake Stitjønn, where the total concentrations of Pb, Cu and Sb were 0.76, 1.8 and 0.12µg/L, respectively. Brown trout (Salmo trutta) from Lake Kyrtjønn had very high levels of Pb in bone (104mg/kg w.w.), kidney (161mg/kg w.w.) and the gills (137mg/kg d.w), and a strong inhibition of the ALA-D enzyme activity were observed in the blood (24% of control). Dry fertilized brown trout eggs were placed in the small outlet streams from Lake Kyrtjønn and the reference lake for 6 months, and the concentrations of Pb and Cu in eggs from the Lake Kyrtjønn stream were significantly higher than in eggs from the reference. More than 90% of Pb accumulated in the egg shell, whereas more than 80% of the Cu and Zn accumulated in the egg interior. Pb in the lake sediments was elevated in the upper 2-5cm layer (410-2700mg/kg d.w), and was predominantly associated with redox sensitive fractions (e.g., organic materials, hydroxides) indicating low potential mobility and bioavailability of the deposited Pb. Only minor amounts of Cu and Sb were deposited in the sediments. The present work showed that the adult brown trout, as well as fertilized eggs and alevins, may be subjected to increased stress due to chronic exposure to Pb, whereas exposure to Cu, Zn and Sb were of less importance. Copyright © 2016 Elsevier Inc. All rights reserved.

Distribution and evolution of Zn, Cd, and Pb in Apollo 16 regolith samples and the average U-Pb ages of the parent rocks

NASA Technical Reports Server (NTRS)

Cirlin, E. H.; Housley, R. M.

1982-01-01

The concentration of surface (low temperature site) and interior (high temperature site) Cd, Zn, and Pb in 13 Apollo 16 highland fines samples, pristine rock 65325, and mare fines sample 75081 were analyzed directly from the thermal release profiles obtained by flameless atomic absorption technique (FLAA). Cd and Zn in pristine ferroan anothosite 65325, anorthositic grains of the most mature fines 65701, and basaltic rock fragments of mare fines 75081 were almost all surface Cd and Zn indicating that most volatiles were deposited on the surfaces of vugs, vesicles and microcracks during the initial cooling process. A considerable amount of interior Cd and Zn was observed in agglutinates. This result suggests that high temperature site interior volatiles originate from entrapment during the lunar maturation processes. Interior Cd found in the most mature fines sample 65701 was only about 15% of the total Cd in the sample. Interior Pb present in Apollo 16 fines samples went up to 60%. From our Cd studies we can assume that this interior Pb in highland fines samples is largely due to the radiogenic decay which occurred after the redistribution of the volatiles took place. We obtained an average age of 4.0 b.y. for the parent rocks of Apollo 16 highland regolith from our interior Pb analyses.

Trace amounts of Cu²⁺ ions influence ROS production and cytotoxicity of ZnO quantum dots.

PubMed

Moussa, Hatem; Merlin, Christophe; Dezanet, Clément; Balan, Lavinia; Medjahdi, Ghouti; Ben-Attia, Mossadok; Schneider, Raphaël

2016-03-05

3-Aminopropyltrimethoxysilane (APTMS) was used as ligand to prepare ZnO@APTMS, Cu(2+)-doped ZnO (ZnO:Cu@APTMS) and ZnO quantum dots (QDs) with chemisorbed Cu(2+) ions at their surface (ZnO@APTMS/Cu). The dots have a diameter of ca. 5 nm and their crystalline and phase purities and composition were established by X-ray diffraction, transmission electron microscopy, UV-visible and fluorescence spectroscopies and by X-ray photoelectron spectroscopy. The effect of Cu(2+) location on the ability of the QDs to generate reactive oxygen species (ROS) under light irradiation was investigated. Results obtained demonstrate that all dots are able to produce ROS (OH, O2(-), H2O2 and (1)O2) and that ZnO@APTMS/Cu QDs generate more OH and O2(-) radicals and H2O2 than ZnO@APTMS and ZnO:Cu@APTMS QDs probably via mechanisms associating photo-induced charge carriers and Fenton reactions. In cytotoxicity experiments conducted in the dark or under light exposure, ZnO@APTMS/Cu QDs appeared slightly more deleterious to Escherichia coli cells than the two other QDs, therefore pointing out the importance of the presence of Cu(2+) ions at the periphery of the nanocrystals. On the other hand, with the lack of photo-induced toxicity, it can be inferred that ROS production cannot explain the cytotoxicity associated to the QDs. Our study demonstrates that both the production of ROS from ZnO QDs and their toxicity may be enhanced by chemisorbed Cu(2+) ions, which could be useful for medical or photocatalytic applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis and characterization of Cu-Zn/TiO2 for the photocatalytic conversion of CO2 to methane.

PubMed

Rana, Adeem Ghaffar; Ahmad, Waqar; Al-Matar, Ali; Shawabkeh, Reyad; Aslam, Zaheer

2017-05-01

Different Cu-Zn/TiO 2 catalysts were synthesized by using the wet impregnation method. The prepared catalysts were used for the conversion of CO 2 into methane by photocatalysis. Various characterization techniques were used to observe the surface morphology, crystalline phase, Brunauer-Emmett-Teller (BET) surface area, presence of impregnated Cu and Zn, and functional group. Scanning electron microscope analysis showed spherical morphology, and slight agglomeration of catalyst particles was observed. BET analysis revealed that the surface area of the catalyst was decreased from 10 to 8.5 m 2 /g after impregnation of Cu and Zn over TiO 2 support. Synergetic effect of Cu and Zn over TiO 2 support (Cu 2.6 /TiO 2 , Zn 0.5 /TiO 2 and Cu 2.6 -Zn 0.5 /TiO 2 ) and the effects of Cu loading (0, 1.8, 2.1, 2.6 and 2.9 wt%) were also investigated at different feed molar ratios of H 2 /CO 2 (2:1 and 4:1). The Cu 2.6 -Zn 0.5 /TiO 2 catalyst showed a maximum conversion of 14.3% at a feed molar ratio of 4. The addition of Zn over the catalyst surface increased the conversion of CO 2 from 10% to 14.3% which might be due to synergy of Cu and Zn over TiO 2 support.

Toxicity of seabird guano to sea urchin embryos and interaction with Cu and Pb.

PubMed

Rial, Diego; Santos-Echeandía, Juan; Álvarez-Salgado, Xosé Antón; Jordi, Antoni; Tovar-Sánchez, Antonio; Bellas, Juan

2016-02-01

Guano is an important source of marine-derived nutrients to seabird nesting areas. Seabirds usually present high levels of metals and other contaminants because the bioaccumulation processes and biotic depositions can increase the concentration of pollutants in the receiving environments. The objectives of this study were to investigate: the toxicity of seabird guano and the joint toxicity of guano, Cu and Pb by using the sea urchin embryo-larval bioassay. In a first experiment, aqueous extracts of guano were prepared at two loading rates (0.462 and 1.952 g L(-1)) and toxicity to sea-urchin embryos was tested. Toxicity was low and not dependent of the load of guano used (EC50 0.42 ± 0.03 g L(-1)). Trace metal concentrations were also low either in guano or in aqueous extracts of guano and the toxicity of extracts were apparently related to dissolved organic matter. In a second experiment, the toxicity of Cu-Pb mixtures in artificial seawater and in extracts of guano (at two loadings: 0.015 and 0.073 g L(-1)), was tested. According to individual fittings, Cu added to extracts of guano showed less toxicity than when dissolved in artificial seawater. The response surfaces obtained for mixtures of Cu and Pb in artificial seawater, and in 0.015 g L(-1) and 0.073 g L(-1) of guano, were better described by Independent Action model adapted to describe antagonism, than by the other proposed models. This implied accepting that EC50 for Cu and Pb increased with the load of guano and with a greater interaction for Cu than for Pb. Copyright © 2015 Elsevier Ltd. All rights reserved.